KR101482287B1 - Emulsion for vibration damping material - Google Patents

Abstract

The present invention is an emulsion for vibration damper containing an emulsion obtained by emulsion polymerization of a monomer component, the emulsion being obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier, wherein the emulsion particles have an average particle diameter of 100 to 450 nm An emulsion for vibration damping material and an acrylic emulsion particle having a core part and a shell part, wherein the acrylic emulsion particle has a Q value in the range of 0.6 to 1.4 and an e value in the range of -0.4 to -1.2 Is formed by polymerizing a monomer component comprising an essential monomer as an essential component.

Description

EMULSION FOR DAMPING MEMBER}

The present invention relates to an emulsion for vibration damping material. More particularly, the present invention relates to an emulsion for vibration damping materials which is useful as a material of a vibration damping material used to prevent vibration and noise in various structures and to maintain static properties.

The vibration damping material is used to prevent vibration and noise in various structures and to maintain the static property. For example, in addition to being used at the bottom of an automobile, etc., a vibration damping material can be used for a railway vehicle, a ship, an aircraft or an electric device, It is widely used in devices and the like. As materials used for such vibration damping materials, conventionally used molded products such as a plate-shaped molded product or a sheet-shaped molded product made of a material having a vibration absorbing performance and a sound-absorbing performance have been used. However, , It is difficult to apply these molded products to the vibration generating point. Therefore, various methods for improving the workability and sufficiently exhibiting vibration damping have been studied. That is, for example, an asphalt sheet containing an inorganic powder has been used in the interior bottom of automobiles, etc. However, since there is a need to heat-seal, there is a need to improve workability and the like, and various compositions for vibration damper And polymers have been studied.

As a substitute material for such a molded workpiece, a coating type vibration damping material (coating material) has been developed. For example, by a coating film formed by spraying by spraying or coating by an arbitrary method, Various vibration damping paints capable of obtaining a vibration absorbing effect and a sound absorbing effect have been proposed. Specifically, for example, in addition to water-based antifouling paints obtained by improving the hardness of a coating film obtained by blending synthetic resin powders with asphalt, rubbers, synthetic resin, etc., synthetic resin powders, And vibration damping paints in which activated carbon is dispersed as a filler in an emulsion. Such vibration damping paints and the like are required to have excellent vibration damping properties and mechanical stability. However, these conventional damping damping paints are still not at a level that can fully satisfy the vibration damping performance, There is a demand for a technique for enabling performance to be achieved. In the case of forming a damping coating film on an adherend, thermal drying is carried out at a high temperature, such as baking, in an actual drying line used industrially, but the conventional damping material emulsion is coated on a vertical surface or a sloped surface , The paint may flow down from the coated surface during or after the thermal drying. For this reason, even when dried in an actual actual drying line, there is no disintegration of the coating film due to deformation of the coating film or the like due to thermal drying, and an excellent film decaying property capable of forming a good coating film on a vertical plane or inclined plane Is required. In addition, since such a vibration-damping coating may be stored and used even in cold regions, it is also required to have excellent low-temperature storage stability so as to maintain a usable state without being frozen even at a low temperature.

As a conventional material for vibration damper, a waterborne vibration damper thickener comprising a polymer having an alkali-soluble monomer unit and a polycarbonate monomer unit is disclosed (for example, see Patent Document 1). The paint containing the waterborne vibration deadening material thickener has excellent drying properties and can sufficiently prevent cracks and swelling on the surface, so that a high-quality vibration damping material excellent in vibration damping property can be imparted, which is industrially useful. However, there has been a room for research to further improve physical properties such as vibration damping property, dryness, mechanical stability, and the like, and to make it more preferable as a material used for vibration damping materials of various structures.

Further, there is disclosed an emulsion composition containing a nonionic compound and a synthetic resin having a molecular weight and the like specified by block and / or randomly adding ethylene oxide and an alkylene oxide having 3 or more carbon atoms to an aliphatic alcohol having 18 or less carbon atoms See Patent Document 2). This composition, however, does not cause liquid sagging even when it is dried at a high temperature. However, since the film thickness at the time of the liquid sagging test is as small as 25 m, the composition capable of forming a coating film with reduced liquid sagging There was room for research.

As the emulsion for vibration damper containing a polymer and an emulsifier, there is disclosed an emulsion for vibration damper which contains 3% by mass or less of a nonionic emulsifier as an emulsifier relative to the total amount of monomers used for forming the polymer (see, for example, 3). This composition can form a coating film in which sagging or deformation is prevented, but there is room for research into a composition in which these effects are more effectively exhibited.

-메틸스티렌 다이머의 존재하에 공중합하여 얻어지는 수계 도료용 공중합체 라텍스 (예를 들어, 특허문헌 5 참조), 공액 디엔계 단량체, 에틸렌계 불포화 카르복실산아미드 단량체나 에틸렌계 불포화 카르복실산 단량체 등을 무기 과황산염계의 중합 개시제의 존재하에 유화 중합하여 얻어지는 내칩핑 도료용 공중합체 라텍스 (예를 들어, 특허문헌 6 참조), 공액 디엔계 단량체, 에폭시기를 갖는 에틸렌계 불포화 단량체나 에틸렌계 불포화 카르복실산알킬에스테르 단량체 등을 유화 중합하여 얻어지는 제진재용 공중합체 라텍스 (예를 들어, 특허문헌 7 참조), 공액 디엔계 단량체, 에폭시기를 갖는 에틸렌계 불포화 단량체나 에틸렌계 불포화 카르복실산아미드 단량체 등을 유화 중합하여 얻어지는 제진재용 공중합체 라텍스 (예를 들어, 특허문헌 8 참조) 가 개시되어 있다. As a composition for vibration damper that forms a conventional vibration damping material, a copolymer latex containing an emulsion is also disclosed. (For example, refer to Patent Document 4), an aliphatic conjugated diene-based monomer, an ethylenically unsaturated carboxylic acid monomer, and the like, which contains at least one type of vehicle-controlling agent selected from synthetic resin emulsions and asphalt emulsions

(For example, see Patent Document 5), a conjugated diene monomer, an ethylenically unsaturated carboxylic acid amide monomer, and an ethylenically unsaturated carboxylic acid monomer, which are copolymerized in the presence of -methylstyrene dimer (See, for example, Patent Document 6), a conjugated diene monomer, an ethylenically unsaturated monomer having an epoxy group, an ethylenically unsaturated carboxyl group, an ethylenically unsaturated monomer having an epoxy group A copolymer latex for vibration damping materials obtained by emulsion-polymerizing an alkyl alkyl ester monomer or the like (see, for example, Patent Document 7), a conjugated diene monomer, an ethylenically unsaturated monomer having an epoxy group, an ethylenically unsaturated carboxylic acid amide monomer, Copolymer latex for vibration damping material obtained by polymerization (see, for example, Patent Document 8 ) Are disclosed.

However, with these techniques, it has not been possible to obtain a vibration damping material that achieves both excellent heat drying and vibration damping properties. That is, in the case of using a synthetic resin emulsion or an asphalt emulsion, since the surface of the coating film is dried by heating and drying, and the moisture in the non-dried coating film tends to evaporate, In the case of using a copolymer latex formed of a conjugated diene monomer and other monomers, the monomer units of the conjugated diene monomer do not fully exhibit vibration damping properties, There has been room for research such as making both heat drying and damping properties compatible.

An aqueous dispersion containing acrylic polymer particles as a composite particle composed of a core part and a dirt layer, which is capable of preparing an aqueous dispersion using a reactive anionic surfactant, and an aqueous dispersion in which such an aqueous dispersion forms a chipping material (See, for example, Patent Document 9).

Since such an aqueous dispersion is preferable for forming the chipping material, the physical properties of the hard coat film, which hardly causes scratches, are emphasized, and the viscosity is set low so that spray coating can be performed. However, as the vibration damping material, it is preferable that the hardness of the coating film is hard, but also the softness is emphasized. In addition, the composition for vibration damper is set to have a relatively high viscosity so as to form a thick coating film. Therefore, there has been room for research such that it can be suitably applied as a composition for vibration damper having such characteristics, excellent vibration damping property and heat drying property, and less time-dependent change.

Also disclosed is an emulsion for vibration damper comprising an emulsion obtained by emulsion polymerization of a monomer component by a reactive emulsifier (see, for example, Patent Document 10). This emulsion for vibration damper is excellent in properties such as vibration damping property and heating dry composition but it is also possible to form a coating film exhibiting high vibration damping property by directly coating not only on the horizontal plane but also on the inclined surface, There was room for.

As the resin emulsion to be used for the vibration damping material, an acrylic emulsion having a core-shell structure is also used. However, the acrylic emulsion tends to cause a delay in the polymerization reaction during the production of the polymer, resulting in mixing of the core / shell polymer composition, which tends to make the localization insufficient. In order to obtain a polymer exhibiting high vibration damping properties by preventing the delay of such polymerization reaction in the past, a polymer having insufficient localization of the composition has not exhibited high vibration damping property, (Meth) acrylate ester is introduced into the reaction system. However, in this method, since the production cost is high, a method for producing an acrylic emulsion which does not cause composition mixing at a lower cost is required.

As a conventional emulsion for vibration damping materials, there is disclosed a copolymer emulsion for vibration damping material obtained by copolymerizing a monomer mixture containing an acrylic monomer as an essential component (see, for example, Patent Document 11). However, since the copolymer emulsion for vibration damper is made of a monomer mixture containing methyl methacrylate in an amount of 25 mass% or more, it is more inexpensive, exhibits high damping property and mechanical stability, And to make it possible to prepare a copolymer emulsion which does not cause mixing of a good composition.

,β-불포화 카르복실산에스테르계 단량체, 방향족 비닐계 단량체 및 디엔계 단량체로 이루어지는 군에서 선택되는 1 종 이상의 단량체와

,β-불포화 카르복실산을 필수 성분으로 하여 얻어지는 합성 수지 에멀션으로서, 유리 전이 온도 (Tg), 손실각 정접의 최대값 및 평균 입자 직경이 특정된 것과, 요소계 화합물, 충전제 및 발포제를 함유하는 제진성 수성 도료 조성물 (예를 들어, 특허문헌 12 참조) 이나, Tg, 손실각 정접 및 수지 입자의 평균 입자 직경이 특정된 수지 에멀션과 충전제를 필수 성분으로 하는 제진성 수성 도료 조성물이 개시되어 있다 (예를 들어, 특허문헌 13 참조). 그러나, 이들 조성물에 대해서도, 더욱 우수한 제진성이나 기계 안정성을 발휘함과 함께, 더욱 저온 저장 안정성도 우수한 조성물로 하는 등의 연구의 여지가 있었다. Also,

,? -unsaturated carboxylic acid ester-based monomer, aromatic vinyl-based monomer, and diene-based monomer and at least one monomer selected from the group consisting of

, and a? -unsaturated carboxylic acid as an essential component, which is characterized in that the glass transition temperature (Tg), the maximum value of the loss angle tangent and the average particle diameter are specified, and that the urea-based compound (See, for example, Patent Document 12), and a vibration-damping aqueous coating composition comprising, as essential components, a resin emulsion and filler whose Tg, loss tangent, and average particle diameter of resin particles are specified (See, for example, Patent Document 13). However, there is room for further research on these compositions, such as a composition which exhibits superior vibration damping properties and mechanical stability, and which is also excellent in low-temperature storage stability.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-137485 (pages 1-2)

Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-257395 (1-2, page 12-13)

Patent Document 3: JP-A-2005-105106 (pages 1-2)

Patent Document 4: JP-A-9-104842 (pages 1-2)

Patent Document 5: JP-A-11-29737 (pages 1-2)

Patent Document 6: Japanese Patent Laid-Open Publication No. 2000-178497 (pages 1-2)

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-178498 (pages 1-2)

Patent Document 8: Japanese Patent Laid-Open Publication No. 2000-178499 (pages 1-2)

Patent Document 9: Specification of Japanese Patent No. 2904995 (Pages 1-3)

Patent Document 10: Japanese Patent Application Laid-Open No. 2004-277603 (pages 1-2)

Patent Document 11: JP-A-2005-281577 (pages 1-2)

Patent Document 12: JP-A No. 2005-187514 (pages 1-2)

Patent Document 13: JP-A-10-324822 (pages 1-2)

DISCLOSURE OF INVENTION

Problems to be solved by the invention

The present invention has been made in view of the above-described phenomenon, and aims at at least one of the following (1) to (3).

(1) Excellent damping property, dryness and mechanical stability in a wide temperature range, and can improve the coating property on the surface of the coating film and can be applied to a vertical surface and used at a high temperature There is provided an emulsion for vibration damping material capable of forming a good coating film sufficiently suppressed from collapse of a coating film due to deformation of a coating film or the like even when it is dried by heat drying.

(2) Excellent vibration damping property and thermal drying property, less time-dependent change, and improved stability and dispersibility of the compound, and excellent vibration damping property even when applied to an adherend having a warp To provide an emulsion for vibration damping material capable of forming a coating film to be exerted.

(3) An emulsion for vibration damping material which contains acrylic emulsion particles having a core part and a shell part, exhibits high vibration damping property in a wide temperature range, and is excellent in mechanical stability and storage stability at a low temperature .

Means for solving the problem

The present inventors have found that when the emulsion for vibration damping material contains an emulsion and an anionic emulsifier, the effect of imparting stability is exerted by the balance of hydrophobic-hydrophilic groups in the structure of the anionic emulsifier, When the diameter is controlled to be within a specific range, the mechanical stability and the pigment dispersibility are remarkably improved, and the vibration damping property and drying property in a wide temperature range are excellent, and the coating on the surface of the coating film as the vibration damper can be improved In addition, it has been found that even when the coating film is dried by thermal drying using a high temperature and applied to a vertical plane, the obtained coating film does not flow down and has a good undercoat film collapsibility.

Further, the present inventors have found that when an emulsion is prepared by emulsion polymerization of a monomer component with a reactive emulsifier, the emulsion becomes less soluble in water, and thus the emulsion exhibits excellent thermal drying properties, the emulsifier has less time- And that the emulsion is chemically bonded to the emulsion, thereby improving the mechanical stability of the emulsion. Furthermore, when such emulsion is controlled so that the particle diameter of the emulsion particles is in a specific range, a good coating film can be formed by applying uniformly to the non-horizontal surface and drying, so that the vibration damping property and mechanical stability It is found that the excellent heat-drying property on the inclined surface capable of forming this excellent coating film is also excellent.

Further, the inventors of the present invention have found that, when the emulsion for vibration damping material contains acrylic emulsion particles having a core portion and a shell portion, as compared with the case where the acrylic copolymer is used singly or when two or more kinds of acrylic copolymers are blended, The present inventors have made various investigations on an acrylic emulsion having a core-shell structure that exhibits excellent damping properties and mechanical stability, and as a result, it has been found that a specific Q value, When an emulsion is formed by using a monomer having an e value as an essential component, it is possible to suppress the mixing of the composition of the core-shell structure and to provide a relatively high Even when the amount of the monomer having Tg is reduced, the core-shell structure in which the mixing of the composition is sufficiently suppressed Found out that there can be produced an acrylic emulsion having a core-shell structure is an acrylic emulsion, that is more expensive than the conventional process for producing the composition of the mix occurs. The acrylic emulsion thus obtained exhibits higher vibration damping properties and excellent mechanical stability in a wide temperature range when used as a vibration damping material, and can be used in a low temperature range without causing freezing or separation of the emulsion. Temperature storage stability capable of maintaining a low temperature storage stability, and it is an object of the present invention to overcome the above problems.

That is, the present invention relates to an emulsion for vibration damper containing an emulsion obtained by emulsion polymerization of a monomer component, wherein the emulsion is obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier, It is an emulsion for vibration damping material of 450 nm.

The present invention also provides an emulsion for vibration damper containing acrylic emulsion particles having a core part and a shell part, wherein the acrylic emulsion particle has a Q value in the range of 0.6 to 1.4 and an e value in the range of -0.4 to -1.2 And is formed by polymerizing a monomer component containing a monomer as an essential component.

Hereinafter, the present invention will be described in detail.

In the present specification, an emulsion for vibration damper containing emulsion having an average particle diameter of 100 to 450 nm obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier is referred to as emulsion (1) for vibration damper of the present invention, . The emulsion (1) for a vibration damping material of the present invention can be obtained by emulsion polymerization using an anionic emulsifying agent, wherein an emulsion (1A) for vibration damping material containing an emulsion having an emulsion particle having an average particle diameter of 100 to 450 nm, , Emulsion 1B for vibration damper containing an emulsion having an average particle diameter of emulsion particles of 100 to 450 nm and emulsion polymerization using an anionic emulsifier and a reactive emulsifier, And three emulsions (1C) for vibration damping materials containing emulsions having an average particle diameter of 100 to 450 nm. The emulsion (1C) for vibration damper of the present invention using an anionic emulsifier and a reactive emulsifier means a type using at least one emulsifier belonging to both an anionic emulsifier and a reactive emulsifier, And a mode of using at least one emulsifier belonging to the emulsifier of the species and the reactive emulsifier. The emulsion (1C) for vibration damper of the present invention is preferably in the form of using at least one emulsifier belonging to any of the anionic emulsifier and the reactive emulsifier.

Further, the emulsion for a vibration damping material containing acrylic emulsion particles having a core part and a shell part is characterized in that the acrylic emulsion particle has a Q value in the range of 0.6 to 1.4 and a monomer having an e value in the range of -0.4 to -1.2 (2) for a vibration damping material according to the present invention is used as the vibration damping material emulsion.

The emulsion for vibration damping material of the present invention satisfies at least one of the formulas (1A), (1B), (1C) and (2), and any one of (1A), (1B) At the same time. Such an effect can exert both of the effects of the emulsions 1A, 1B and 1C for vibration damping materials of the present invention and the effects of the emulsion 2 for vibration damping materials of the present invention. More preferably, (1C) and (2) are satisfied at the same time.

In the following description, the term " emulsion for vibration damper of the present invention " includes both of the emulsion (1) and (2) for vibration damper of the present invention. That is, the description of the "emulsion for vibration damper of the present invention" is applicable to any of the emulsion (1) and (2) for vibration damper of the present invention. In the case of "anionic emulsifier and / or reactive emulsifier", the emulsion 1A for vibration damping material of the present invention means only an anionic emulsifier, while the emulsion 1B for vibration damping material of the present invention means only a reactive emulsifier And the term "emulsion (1C)" for vibration damping material of the present invention means an anionic emulsifier and a reactive emulsifier.

First, the emulsion 1 for vibration damping material of the present invention will be described below.

The emulsion (1) for vibration damper of the present invention contains an emulsion obtained by emulsion-polymerizing a monomer component using an anionic emulsifier and / or a reactive emulsifier, but may contain one kind of such an emulsion or two or more kinds of such emulsions . As long as it contains at least one emulsion obtained by emulsion-polymerizing a monomer component by using an anionic emulsifier and / or a reactive emulsifier, an emulsion other than the emulsion obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier It is preferable that the emulsion obtained by emulsion-polymerizing the monomer component by using an anionic emulsifier and / or a reactive emulsifier is at least 50% by mass based on the total amount of the emulsion of 100% by mass. More preferably, it is 80 mass% or more. As the other emulsions, other emulsion resins described later and the like can be used.

The emulsion (1) for the vibration damping material is a polymer obtained by emulsion-polymerizing a monomer component by using an anionic emulsifier and / or a reactive emulsifier in the form of particles dispersed in a medium. The medium is preferably an aqueous medium, for example, water or a mixed solvent of water and water and a mixed solvent of water and the like. Among them, water is preferable in view of safety and environmental effects when applying the coating material containing the emulsion (1) for vibration damper of the present invention.

The content ratio of the emulsion particles obtained by emulsion-polymerizing the monomer component using the nonvolatile matter in the emulsion 1 for the vibration damping material, that is, the anionic emulsifying agent and / or the reactive emulsifier is preferably 100% By mass to 70% by mass or less based on the total mass of the resin composition. If it exceeds 70% by mass, the viscosity of the emulsion 1 for vibration damper becomes too high, and sufficient dispersion stability may not be maintained, which may cause aggregation. If it is less than 30% by mass, sufficient vibration damping property may not be exhibited. More preferably, it is 50 mass% or more and 65 mass% or less.

When the emulsion (1) for vibration damping material contains other emulsions other than the emulsion obtained by emulsion-polymerizing the monomer components using an anionic emulsifier and / or a reactive emulsifier, an anionic emulsifier and / or a reactive emulsifier is used The nonvolatile fraction of the entire emulsion (1) for vibration damping material of the present invention containing an emulsion obtained by emulsion polymerization of a monomer component and other emulsions is also preferably the above ratio.

The emulsion (1) for vibration damper of the present invention has emulsion particles obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier having an average particle diameter of 100 to 450 nm.

By using the emulsion particles having an average particle diameter in this range, the obtained coating film does not flow down even after the thermal drying, and has good undercoat film disintegratability. Therefore, A film can be formed.

The average particle diameter of the emulsion particles is preferably 120 to 400 nm. More preferably 150 to 350 nm. When the average particle diameter of the emulsion particles is in this range, the action and effect of the emulsion 1 for vibration damping material of the present invention can be exerted more effectively.

The emulsion (1) for vibration damper of the present invention may contain an emulsion obtained by emulsion polymerization of a monomer component by using an anionic emulsifier and / or a reactive emulsifier and other emulsions. In this case, both of these emulsions The average particle diameter of the emulsion contained is preferably 100 to 450 nm. That is, the average particle diameter of the entire emulsion (1) for vibration damping material of the present invention is also preferably in the above range.

For example, the emulsion was diluted with distilled water and sufficiently stirred, and about 10 ml of the emulsion was collected in a glass cell. The particle size was measured with a particle size distribution analyzer (NICOM P Model 380, Particle Sizing Systems, ). ≪ / RTI >

In the emulsion (1) for vibration damping material of the present invention, the emulsion particles having the average particle diameter have a particle size distribution defined by a value obtained by dividing the standard deviation by the volume average particle diameter (standard deviation / volume average particle diameter x 100) % Or less. More preferably, it is 30% or less. If the particle size distribution exceeds 40%, the width of the particle diameter distribution of the emulsion particles becomes very wide, and coarse particles are contained in a part thereof. Therefore, the emulsion for vibration damper is coated with sufficient inclination There is a fear that the dry buildup can not be exerted.

The emulsifier used in the production of the emulsion 1 for vibration damper may contain an anionic emulsifier or an emulsifier other than the reactive emulsifier as long as it contains an anionic emulsifier and / or a reactive emulsifier, but an anionic emulsifier and / The emulsifier is preferably the main component of the emulsifier. More preferably, all of the emulsifiers are anionic emulsifiers and / or reactive emulsifiers. By using an anionic emulsifier and / or a reactive emulsifier as an emulsifier, it is possible to suppress the thermal expansion during drying due to the emulsifier being liberated in water and bleeding to the surface of the coating film, and to improve the stability and dispersibility of the emulsion Thereby enhancing the vibration damping property.

The emulsion (1) for a vibration damping material of the present invention comprises 1.0 part by weight or more of an anionic emulsifier (A) based on 100 parts by weight of the total amount of monomer components used in the production of an emulsion obtained by emulsion polymerization of a monomer component using an anionic emulsifier and / And / or a reactive emulsifier. If the amount is less than 1.0 part by weight, excellent drying and vibration damping properties can not be exhibited, and the pigment miscibility at the time of mixing with the pigment may be insufficient, which may not be useful as a vibration damping material for various structures. Preferably 2.0 parts by weight or more, and more preferably 2.5 parts by weight or more. In view of economical efficiency, it is preferable that the amount is 5.0 parts by weight or less.

When both the anionic emulsifier and the reactive emulsifier are used, it is preferable that the total amount satisfies the above range.

The anionic emulsifier used in the emulsion (1) for vibration damping materials is a sulfate compound or a succinate salt compound. The sulfate compound is at least one member selected from the group consisting of aliphatic alkyl groups having 8 or more carbon atoms, oleyl groups, alkylphenyl groups, styryl groups and benzyl groups It is preferable that the group has a species group. The aliphatic alkyl group having 8 or more carbon atoms preferably has 12 or more carbon atoms or 1 or more aromatic rings.

Among them, preferred are polyoxyalkylene alkyl ether sulfuric acid ester salts, polyoxyalkylene oleyl ether sulfuric acid sodium salts, polyoxyalkylene alkylphenyl ether sulfuric acid ester salts, alkyl diphenyl ether disulfonic acid salts, polyoxyalkylene (mono, di (Tri-) styrylphenyl ether sulfuric acid ester salt, polyoxyalkylene (mono-, di- tri-) benzylphenyl ether sulfuric acid ester salt and alkenylsuccinic acid di-salt.

Since all of these anionic emulsifiers have strong hydrophobic skeletons, they all have the same effect. By using these anionic emulsifiers, the properties of the emulsion 1 for vibration damping materials of the present invention can be more effectively exhibited.

The polyoxyalkylene (mono, di, tri) styrylphenyl ether sulfuric acid ester salts include polyoxyalkylene monostyryl phenyl ether sulfuric acid ester salts, polyoxyalkylene distyryl phenyl ether sulfuric acid ester salts, polyoxyalkyl (Mono, di (tri) benzylphenyl ether sulfuric acid ester salt) means a polyoxyalkylene monobenzylphenyl ether sulfuric acid ester salt, a polyoxyalkylene dibenzyl ester Phenyl ether sulfuric acid ester salt, and polyoxyalkylenetribenzylphenyl ether sulfuric acid ester salt.

As the anionic emulsifier used in the emulsion 1 for vibration damping materials, among the above-mentioned anionic emulsifiers, polyoxyethylene alkyl ether sulfuric acid ester salts having an average addition mole number of 15 to 35 and polyoxyethylene alkyl ether sulfuric acid ester salts having an ethylene oxide chain, At least one member selected from the group consisting of polyoxyethylene (mono, di (tri) styrylphenyl ether sulfuric acid ester salt and polyoxyethylene (mono, di (tri) benzylphenyl ether sulfuric acid ester salt) . Emulsion A-60, Emulsion A-60, B-66 (manufactured by Kao Corporation), Newcol 707SF (manufactured by Kao Corporation), and the like are particularly preferable as the anionic emulsifier. , ABC-2010, 2020, 2030, DSB (manufactured by Rhodia Nikka), Adekariosoft SR-10, NKCOL 707SN, NewCol 714SF, NewCol 714SN, Antox MS- SR-20, SR-30 (manufactured by ADEKA), and the like. Surfactants corresponding to these nonionic types can also be used.

Among these, an anionic emulsifier which is not a reactive emulsifier is most preferable as Latte water WX.

In the emulsion 1 for vibration damping materials, other commonly used anionic emulsifiers may be used in combination with at least one of the above-mentioned anionic emulsifiers. Examples of such anionic emulsifiers include, but are not limited to, alkylsulfate salts such as sodium dodecylsulfate, potassium dodecylsulfate, and ammonium alkylsulfate; sodium dodecylpolyglycol ether sulfates; sodium sulfosilicate Alkyl sulphonates such as sodium dodecylbenzenesulfonate and alkali metal sulphates of alkali phenol hydroxyethylene, high alkyl naphthalenesulfonate salts, naphthalenesulfonic acid formalin condensates, sodium laurate , Fatty acid salts such as triethanolamine oleate and triethanolamine abietate, polyoxyalkyl ether sulfuric acid ester salts, polyoxyethylene carboxylic acid ester sulfuric acid ester salts, polyoxyethylene phenyl ether sulfuric acid ester salts and succinic acid dialkyl ester sulfonic acid salts ; Polyoxyethylene alkylarylsulfate salts and the like The two or more thereof are preferred.

As the anionic emulsifier, a reactive anionic surfactant, a sulfosuccinate type reactive anionic surfactant, and an alkenylsuccinate type reactive anionic surfactant may be used as a reactive emulsifier.

Examples of commercial products of sulfosuccinate type reactive anionic surfactants include Latex S-120, S-120A, S-180 and S-180A (all trade names, manufactured by Kao Corp.), Eliminol JS-2 (trade name, And the like. Examples of commercial products of alkenylsuccinic acid salt type reactive anionic surfactants include Latte water ASK (trade name, manufactured by Kao Corporation) and the like.

As the anionic emulsifier, the following surfactants and the like are also preferable as the reactive emulsifier.

(1 to 4) ester salt type surfactants of aliphatic unsaturated carboxylic acids having 3 to 5 carbon atoms such as 2-sulfoethyl (meth) acrylate sodium salt, 3-sulfopropyl (meth) acrylate ammonium salt (Meth) acrylic acid sulfoalkyl ester salt type surfactants such as sulfopropyl maleate alkyl ester sodium salt, sulfopropyl maleic acid polyoxyethylene alkyl ester ammonium salt, and sulfoethyl fumaric acid polyoxyethylene alkyl ester ammonium salt; A carboxylate alkylsulfoalkyl diester salt type surfactant.

(Meth) acrylate sulfuric acid ester salt, 1-allyloxy-3-alkylphenoxy-2-polyoxyethylenesulfuric ester salt (trade name: AH), maleic acid dipropylene glycol ester alkylphenol ether sulfuric acid ester salt, phthalic acid dihydroxyethyl ester Decarylsof SE-10N, manufactured by Asahi Denka Kogyo K.K.) and polyoxyethylene alkylalkenylphenol sulfuric acid ester salt (trade name: Aquaron, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.).

As the reactive emulsifier contained in the emulsion for vibration damping material (1), anionic emulsifying agent having a polymerizable group, nonionic emulsifying agent and the like are preferably used, and one or more of them can be used. Among these, (Meth) acryloyl groups, propenyl groups, and the like.

Examples of the anionic emulsifier having a polymerizable group for use in the production of the emulsion (1) for vibration damping material of the present invention include, in addition to the specific examples of the anionic emulsifier, (meth) acrylic acid polyoxyethylene sulfonate (E.g., Ellinol RS-30 manufactured by Sanyo Chemical Industries, Ltd.), a sulfonate salt of allyloxymethylalkyloxypolyoxyethylene (e.g., Aquaron KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , Etc.) and ammonium polyoxyalkylenealkenyl ether sulfate (e.g., " Latex PD-104 ", manufactured by Kao Corp.) and the like are preferable.

Examples of the nonionic emulsifier having a polymerizable group for use in the production of the emulsion (1) for vibration damper of the present invention include allyloxymethylalkoxyethylhydroxypolyoxyethylene (for example, " Adeka (For example, "Latex PD-420" and "Latex PD-430" manufactured by Kao Corp.) and the like are preferable.

Examples of the reactive emulsifier used in the production of the emulsion (1) for vibration damping material of the present invention include among others, Antox MS-60 (trade name, manufactured by Nippon Oil & , 30 (trade name, manufactured by Asahi Denka Kogyo K.K.), Aquaron KH-10 (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) and Latex PD-104 (trade name, manufactured by Kao Corporation).

By using emulsions obtained by using these reactive emulsifiers, the properties of the emulsion for vibration damper of the present invention can be more effectively exerted.

Among the above reactive emulsifiers, it is preferable to use a reactive emulsifier having an ethylene oxide addition structure, since the emulsion for vibration damper is excellent in kneading property with pigments, fillers and the like. The stability of pigments, fillers and the like is improved by the addition structure of ethylene oxide.

In the emulsion (1) for vibration damping material of the present invention, the amount of the reactive emulsifier to be used is 0.1 to 10 mass% with respect to the amount of the compound containing the total polymerizable unsaturated bonding group. If it is less than 0.1% by mass, the mechanical stability can not be sufficiently improved, and the polymerization stability may not be maintained sufficiently. More preferably from 0.5 to 5% by mass, and most preferably from 1 to 3% by mass.

The emulsion constituting the emulsion 1 for vibration damper of the present invention will be described below.

As the emulsion constituting the emulsion 1 for vibration damping material of the present invention, those which are usually used may be used, and those containing one or more kinds of polymers are preferable.

Such a polymer is usually present in a form dispersed in a medium. That is, it is preferable that the emulsion has a medium and a polymer dispersed in the medium. The medium is preferably an aqueous medium, and examples thereof include water, a mixed solvent of one or more kinds of solvents which can be mixed with water, a mixed solvent in which water is a main component, . Among them, water is preferable in view of safety and environmental impact when applying the paint containing the emulsion for vibration damper of the present invention.

The monomer component to be the raw material of the emulsion constituting the emulsion for vibration damping material (1) in the present invention is not limited so long as it can exert the action and effect of the present invention. It is preferable that the monomer component contains the unsaturated carboxylic acid-based monomer. More preferably an unsaturated carboxylic acid-based monomer and other monomers copolymerizable with the unsaturated carboxylic acid-based monomer. The unsaturated carboxylic acid-based monomer is not particularly limited as long as it is a compound having an unsaturated bond and a carboxyl group in the molecule and a derivative thereof such as a salt or ester thereof, but preferably contains an ethylenically unsaturated carboxylic acid-based monomer. That is, an emulsion for vibration damper comprising an emulsion obtained by polymerizing a monomer component containing an ethylenically unsaturated carboxylic acid monomer as an essential component is one of preferred embodiments of the present invention.

When the emulsion particle of the present invention is an emulsion particle having a core part and a shell part, which will be described later, the other monomer copolymerizable with the unsaturated carboxylic acid-based monomer and the unsaturated carboxylic acid-based monomer is a monomer component forming the core part of the emulsion, May be contained in any of the monomer components to be formed, and may be used for all of them.

The ethylenically unsaturated carboxylic acid monomer is not particularly limited and examples thereof include (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, , Monoethylmaleate, and the like, or derivatives thereof, and the like.

Of these, (meth) acrylic monomers are preferred. (Meth) acrylic monomer means a (meth) acrylic acid derivative such as a salt of (meth) acrylic acid and (meth) acrylic acid or a (meth) acrylic acid ester.

That is, the emulsion constituting the emulsion 1 for vibration damper of the present invention is preferably an acrylic copolymer.

In the present invention, " acrylic copolymer " means a copolymer obtained by using at least two kinds of monomer components, and at least one of the monomer components means a copolymer which is a (meth) acrylic monomer. Among them, those obtained by using a monomer component containing a (meth) acrylic acid-based monomer are preferable. (Meth) acrylic acid-based monomer means (meth) acrylic acid and its salt. That is, in the acrylic copolymer of the present invention, at least one of the monomer components is C (R ¹ ₂ ) = CH-COOR ² or C (R ³ ₂ ) = C (CH ₃ ) -COOR ⁴ (R ¹ , R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, a metal atom, an ammonium group, or an organic amine group).

The monomers constituting the raw material of the acrylic copolymer include those containing 0.1 to 20 mass% of a (meth) acrylic acid-based monomer and 99.9 to 80 mass% of other copolymerizable ethylenically unsaturated monomers relative to 100 mass% of the total monomer component desirable. (Meth) acrylic acid-based monomer, the dispersibility of the filler such as inorganic powder is improved in the vibration damper blend containing the emulsion for vibration damper of the present invention, and the vibration damping property is further improved. Further, by containing the other copolymerizable ethylenically unsaturated monomer, it is easy to adjust the acid value, Tg, physical properties, and the like of the emulsion. Even if the (meth) acrylic acid-based monomer is less than 0.1% by mass or more than 20% by mass, the emulsion may not be stably copolymerized in the monomer component. In the emulsion of the present invention, the heat drying property and vibration damping property of the water-based vibration damping material can be sufficiently exhibited by the synergistic effect of the monomer units formed from these monomers.

More preferably 0.5 to 3% by mass of a (meth) acrylic acid-based monomer and 99.5 to 97% by mass of other copolymerizable ethylenically unsaturated monomers relative to 100% by mass of the total monomer component.

Other copolymerizable ethylenically unsaturated monomers include (meth) acrylic monomers other than the (meth) acrylic acid monomers described below, unsaturated monomers having nitrogen atoms, unsaturated compounds having aromatic rings, Outside monomers are included.

Examples of the (meth) acrylic acid monomers used as the raw material of the acrylic copolymer include acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, Malic acid and the like are preferably used.

Examples of the (meth) acrylic monomers other than the (meth) acrylic acid monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, iso Propyl methacrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, Acrylate, isoamyl methacrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl methacrylate, isooctyl acrylate, isooctyl methacrylate Acrylate, nonyl acrylate, nonyl methacrylate, isononyl acrylate, Octyl methacrylate, hexyl acrylate, octyl methacrylate, octyl methacrylate, octyl methacrylate, octyl methacrylate, octyl methacrylate, octyl methacrylate, decyl acrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, Ethylhexyl acrylate, 2-ethylhexyl methacrylate, vinyl formate, vinyl acetate, vinyl propionate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-heptyl acrylate, Hydroxypropyl methacrylate, diallyl phthalate, triallyl cyanurate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol diacrylate, Butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, di Ethylene glycol dimethacrylate, allyl acrylate, allyl methacrylate and the like, and salts and esterified products thereof are preferably used.

The salt is preferably a metal salt, an ammonium salt, an organic amine salt or the like. Examples of the metal atom forming the metal salt include monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; bivalent metal atoms such as alkaline earth metal atoms such as calcium and magnesium; And preferable examples of the organic amine salt include an alkanolamine salt such as an ethanolamine salt, a diethanolamine salt, and a triethanolamine salt, or a triethylamine salt.

-메틸스티렌, 비닐톨루엔, 에틸비닐벤젠 등의 방향 고리를 갖는 불포화 화합물, 아크릴로니트릴, 메타크릴로니트릴, 아크릴아미드, 메타크릴아미드, 디아세톤아크릴아미드, N-메틸올아크릴아미드, N-메틸올메타크릴아미드, N-메톡시메틸(메트)아크릴아미드, N-메톡시에틸(메트)아크릴아미드, N-n-부톡시메틸(메트)아크릴아미드, N-i-부톡시메틸(메트)아크릴아미드 등의 질소 원자를 갖는 불포화 화합물 등을 들 수 있다. The monomer component may further contain other monomers copolymerizable with the (meth) acrylic acid-based monomer. Other monomers include, for example, divinylbenzene, styrene,

Unsaturated compounds having aromatic rings such as methylstyrene, vinyltoluene and ethylvinylbenzene; unsaturated compounds having aromatic rings such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, (Meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl And an unsaturated compound having a nitrogen atom.

It is preferable that the monomer component serving as a raw material of the acrylic copolymer contains 20 mass% or more of the (meth) acrylic monomer based on 100 mass% of the total monomer component. More preferably, it is 30 mass% or more.

Of the other copolymerizable ethylenically unsaturated monomers, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N Unsaturated compounds having a nitrogen atom such as methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide and Ni-butoxymethyl In the monomer component is preferably 40 mass% or less based on 100 mass% of the total monomer component. More preferably, it is 20 mass% or less.

In the emulsion (1) for vibration damping material of the present invention, it is preferable that the monomer component forming the acrylic copolymer contains at least one polymerizable monomer having a glass transition temperature of 0 占 폚 or lower of the homopolymer. More preferably at least two kinds, and most preferably, each monomer component used in each step of the multistage polymerization contains one kind of a polymerizable monomer having a glass transition temperature of 0 占 폚 or less of the homopolymer. As the polymerizable monomer having a glass transition temperature of 0 占 폚 or lower of the homopolymer, butyl acrylate and 2-ethylhexyl acrylate are preferable.

That is, in the present invention, the monomer component forming the emulsion particle obtained by emulsion-polymerizing the monomer component by using the anionic emulsifier and / or the reactive emulsifier is one containing butyl acrylate and / or 2-ethylhexyl acrylate . If the monomer component comprises butyl acrylate and / or 2-ethylhexyl acrylate, the vibration damping property in a wide temperature range is improved.

More preferably, the monomer component contains butyl acrylate and 2-ethylhexyl acrylate.

When the monomer component forming the acrylic copolymer contains butyl acrylate, the content of butyl acrylate is preferably 10 to 60 mass% with respect to 100 mass% of the monomer component forming the acrylic copolymer. More preferably from 20 to 50% by mass.

When the monomer component contains 2-ethylhexyl acrylate, the content of 2-ethylhexyl acrylate is preferably 5 to 55% by mass based on 100% by mass of the monomer component forming the acrylic copolymer. And more preferably 10 to 50% by mass.

In the case of containing both butyl acrylate and 2-ethylhexyl acrylate, the content of the total of butyl acrylate and 2-ethylhexyl acrylate is preferably 20 to 70% by weight based on 100% by weight of the monomer component forming the acrylic copolymer % By mass. And more preferably 30 to 60 mass%.

It is preferable that the monomer component forming the acrylic copolymer further contains less than 10% by mass of an unsaturated monomer having a functional group with respect to the entire monomer component. The functional group in the unsaturated monomer having a functional group may be a functional group capable of crosslinking when an emulsion is obtained by polymerization. By the action of such a functional group, it is possible to improve the film formability of the emulsion and the drying dryness. And more preferably 0.1 to 3.0 mass%.

The mass ratio is a mass ratio to 100 mass% of the total monomer component.

Examples of the functional group of the unsaturated monomer having a functional group include an epoxy group, an oxazoline group, a carbodiimide group, an aziridinyl group, an isocyanate group, a methylol group, a vinyl ether group, a cyclocarbonate group, . These functional groups may be contained in one molecule of the unsaturated monomer or may be two or more.

Examples of the unsaturated monomer having a functional group include divinylbenzene, ethylene glycol di (meth) acrylate, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) (Meth) acrylamide, N-methylol (meth) acrylamide, diallyl phthalate, diallyl terephthalate, polyethylene glycol di (meth) acrylate, propylene glycol Acrylate such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, , And neopentyl glycol di (meth) acrylate; glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate and acryl glycidyl ether. Among them, it is preferable to use an unsaturated monomer having two or more functional groups (multifunctional unsaturated monomer). These may be used alone or in combination of two or more.

The glass transition temperature (Tg) of the acrylic copolymer, that is, the emulsion obtained by emulsion polymerization with an anionic emulsifier and / or a reactive emulsifier is preferably -20 to 30 ° C. As a result, it is possible to exhibit higher vibration damping properties under a wide temperature range. More preferably -10 to 20 占 폚.

Further, the Tg of the acrylic copolymer may be determined on the basis of the knowledge already obtained, and may be controlled by the kind and the use ratio of the monomer component. Theoretically, the Tg of the acrylic copolymer can be calculated from the following calculation formula.

[Equation 1]

In the formula, Tg 'is the Tg (absolute temperature) of the acrylic copolymer. W ₁ ', W ₂ ', ... W ' _n is the mass fraction of each monomer relative to the total monomer component. T ₁ , T ₂ , ... T _n is the glass transition temperature (absolute temperature) of the homopolymer (homopolymer) comprising each monomer component.

When two or more kinds of acrylic copolymers are used as the acrylic copolymer, those having different Tg are preferably used. By forming a difference in the glass transition temperature (Tg) in this way, higher vibration damping properties can be exhibited under a wide temperature range, and vibration durability particularly in the practical range of 20 to 60 DEG C is remarkably improved. When three or more kinds of acrylic copolymers are used, at least two kinds of acrylic copolymers may be different from each other in Tg, and with respect to the remaining one or more types, any one of the two types of acrylic copolymers may have the same Tg .

The Tg difference is preferably 10 to 60 占 폚 when the acrylic copolymer having different Tg is referred to as "acrylic copolymer (A)" having a higher Tg and the lower one as "acrylic copolymer (B)". If the temperature difference is less than 10 占 폚 or the temperature difference is too large, there is a possibility that the vibration damping property in practical range may not be sufficient. It is more preferably 15 to 55 ° C, and still more preferably 20 to 50 ° C.

The glass transition temperature (TgA) of the acrylic copolymer (A) is preferably 0 deg. C or more and 50 deg. C or less. More preferably, the Tg is 0 占 폚 or higher and 30 占 폚 or lower. As a result, the drying property of the damping material coating film formed by using the coating material containing the emulsion 1 for the vibration damping material of the present invention becomes satisfactory, and expansion and cracks on the surface of the coating film are sufficiently suppressed. That is, a vibration damping material having a remarkably excellent vibration damping property is formed. More preferably 5 DEG C or more.

The glass transition temperature (TgB) of the acrylic copolymer (B) is preferably -50 ° C or higher and 10 ° C or lower. More preferably -20 ° C or more and 0 ° C or less.

As the acrylic copolymer (A), it is preferable to use an emulsion obtained by emulsion-polymerizing a monomer component by an anionic emulsifier and / or a reactive emulsifier in the present invention. As the acrylic copolymer (B) An emulsion containing an emulsifier and / or a reactive emulsifier may be used, but is not particularly limited and a commercially available product may be used.

The acrylic copolymer preferably has a weight average molecular weight of 20,000 to 250,000. If the weight average molecular weight is less than 20,000, the vibration damping property is not sufficient, and furthermore, the resulting emulsion for vibration damper may not be excellent in stability in a state in which it is blended with the paint. If it exceeds 250,000, for example, when two or more kinds of acrylic copolymers are used, the compatibility is not sufficient, so that the balance of the vibration damping property can not be maintained sufficiently, and the damping property in the region of 30 to 40 占 폚 may not be improved in particular And there is a possibility that the film-forming at a low temperature in a state in which it is blended with a coating may not be sufficient. Preferably from 30,000 to 200,000, and more preferably from 40,000 to 200,000.

The weight average molecular weight can be determined by GPC (Gel Permeation Chromatography) measurement under the following measurement conditions, for example.

Measuring instrument: HLC-8120GPC (trade name, manufactured by Toso Co., Ltd.)

Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (all manufactured by Toso Co., Ltd.) are connected in series and used

Eluent: tetrahydrofuran (THF)

Standard material for calibration curve: polystyrene (manufactured by Tosoh Corporation)

Measuring method: The object to be measured is dissolved in THF so that the solid content is about 0.2 mass%, and the filtered sample is used as a measurement sample to measure the molecular weight.

The pH of the emulsion obtained by emulsion-polymerizing the monomer component using the above-mentioned anionic emulsifier and / or reactive emulsifier is not particularly limited, but is preferably 2 to 10, more preferably 3 to 9, for example. The pH of the emulsion can be adjusted by adding ammonia water, water-soluble amines, aqueous alkali hydroxide solution or the like to the emulsion.

The viscosity of the emulsion obtained by emulsion-polymerizing the monomer component using the above-mentioned anionic emulsifier and / or reactive emulsifier is not particularly limited, but is preferably 10 to 10000 mPa · s, more preferably 50 to 10000 mPa · s, 5000 mPa 占 퐏.

The viscosity can be measured using a B-type rotational viscometer at 25 캜 and 20 rpm.

The emulsion particles obtained by emulsion polymerization by the anionic emulsifier and / or the reactive emulsifier in the present invention are preferably emulsion particles having a core portion and a shell portion. If the emulsion is of this type, the emulsion 1 for vibration damping material of the present invention exerts a more excellent effect. The emulsion having the core portion and the shell portion has excellent vibration damping properties over a wide range within the practical temperature range. In particular, even in the high-temperature region, the vibration damping material exhibits excellent damping properties as compared with other vibration damping material blends, and as a result, the vibration damping performance can be exhibited over a wide range from a normal temperature to a high temperature range within a practical temperature range.

When the emulsion is of such a kind, the core portion and the shell portion may be completely homologous to each other so that they can not be distinguished from each other, and they may be completely incompletely used to form a core-shell composite structure or a microdomain structure .

Of these structures, a core-shell composite structure is preferable in order to sufficiently draw the characteristics of the emulsion and to produce a stable emulsion.

In the core-shell composite structure, it is preferable that the surface of the core portion is covered with the shell portion. In this case, it is preferable that the surface of the core portion is completely covered with the shell portion. Alternatively, the core portion may be covered with a mesh-like shape or the core portion may be exposed.

In the emulsion particle having the core part and the shell part, the polymer forming the core part and the polymer part forming the shell part can be obtained, for example, by weight average molecular weight, glass transition temperature, SP value (solubility coefficient), kind of monomer used, And the use ratio of the inorganic filler. Among them, those having a difference in at least one of a weight average molecular weight and a glass transition temperature are preferable.

When the emulsion particle is an emulsion particle having a core portion and a shell portion, the difference between the glass transition temperature (Tg) of the monomer component forming the core portion and the monomer component forming the shell portion is preferably 10 to 60 ° C. When the difference in Tg is less than 10 占 폚 or when it is greater than 60 占 폚, vibration damping property in a wide temperature range (20 占 폚 to 60 占 폚) may not be obtained. More preferably, the difference in Tg is from 15 to 55 ° C, and more preferably from 20 to 50 ° C. The Tg of the monomer component forming the core portion is preferably higher than the Tg of the monomer component forming the shell portion. That is, in the case of producing an emulsion having a core portion and a shell portion, the emulsion of the core portion is formed and then the emulsion of the shell portion is formed by multi-stage polymerization. The Tg of the monomer component used in the pre- Is higher than the Tg of the monomer component used in the process. In the case where the emulsion is produced by the three or more steps, it is also preferable that the Tg of the monomer component used in the post-process is lower than the Tg of the monomer component used in the immediately preceding process.

In the emulsion particle having the core portion and the shell portion, it is preferable that the mass ratio of the monomer component forming the core portion to the monomer component forming the shell portion is 20/80 to 70/30. When the mass ratio of the monomer component forming the core part is smaller than 20/80 or larger than 70/30, the vibration damping property in a wide temperature range can not be obtained.

The emulsion (1) for a vibration damping material of the present invention may be blended with an emulsion obtained by emulsion polymerization of a monomer component by using an anionic emulsifier and / or a reactive emulsifier and other emulsion resins. In this case, The same function and effect can be obtained. Examples of the other emulsion resins include acrylic resins, urethane resins, SBR resins, epoxy resins, vinyl acetate resins, vinyl acetate-acrylic resins, vinyl chloride resins, vinyl chloride-acrylic resins, vinyl chloride- Resin, a vinylidene chloride resin, a styrene-butadiene resin, and an acrylonitrile-butadiene resin.

In this case, the mass ratio (emulsion / other emulsion resin obtained by emulsion polymerization of monomer components using an anionic emulsifier and / or a reactive emulsifier) of the emulsion obtained by emulsion polymerization of the monomer component by using an anionic emulsifier and other emulsion resin, Is set to be in the range of 100 to 50/0 to 50.

As a method for producing an emulsion constituting the emulsion (1) for vibration damper of the present invention, the monomer component is polymerized by the emulsion polymerization method in the presence of an anionic emulsifier and / or a reactive emulsifier. For example, by appropriately adding a monomer component, a polymerization initiator and an anionic emulsifier and / or a reactive emulsifier to an aqueous medium and polymerizing them. It is preferable to use a polymerization chain transfer agent or the like for controlling the molecular weight.

As the anionic emulsifier and / or the reactive emulsifier, those described above may be used. Further, when the emulsion polymerization is carried out, other emulsifiers may be used together with the anionic emulsifier and / or the reactive emulsifier. As other emulsifiers, one or more of nonionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants can be used.

As a method of controlling the average particle diameter of the emulsion to the above-mentioned preferable range, a method of adding seed particles to a part of a monomer component in an aqueous solvent such as water to form emulsion particles by adding the remaining monomer components Method is preferable. Since the average particle diameter of the emulsion is influenced by the number of seed particles in the aqueous medium, the number of seed particles is controlled by suitably adjusting the amount of the monomer component added to the aqueous medium to form the seed particles, Can be set within the above-described preferable range.

The monomer emulsion comprising water, an emulsifier and a polymerizable monomer injected directly into the polymerization reactor to form the seed particles is 0.5 to 10 mass% of the total feed amount. In addition, a method of injecting only the emulsifier aqueous solution directly into the polymerization reactor is also one of preferred methods, and it is preferable that the total polymerization monomer is used in an amount of 0.1 to 1.5% by mass in terms of emulsion solid content.

It is also important to control so as not to generate new particles after generation of the seed particles. In order to produce the above-mentioned emulsion having the above-described particle size distribution of 5 to 40% as the emulsion constituting the vibration damping material for vibration damping material (1), it is necessary to always ensure a reaction rate of a certain value or more. Specifically, Is injected into a polymerization kiln and an initial polymerization reaction is carried out to form seed particles. The polymerization rate measured at the end of the initial reaction is preferably 80% or more, more preferably 90% or more. The reaction rate can be measured as the ratio of the measured solid content to the theoretical solid content calculated from the amount of the raw material used in the process after sampling 30 minutes after the completion of the reaction process.

The emulsion thus obtained is one of the preferred embodiments of the present invention.

Also, as a method for producing the emulsion 1 for vibration damper as described above, there is also a method for producing an emulsion for vibration damper which emulsifies and polymerizes a monomer component using an anionic emulsifier and / or a reactive emulsifier while controlling the particle diameter of the emulsion particle It is also one of the present invention.

When the emulsion constituting the emulsion 1 for vibration damping material of the present invention is an emulsion having a core part and a shell part, it is preferably obtained by a conventional emulsion polymerization method. Concretely, there is a method in which a monomer component is emulsion-polymerized in an aqueous medium in the presence of an emulsifier and / or a protective colloid to form a core part, and then the monomer component is emulsion-polymerized in addition to the emulsion containing the core part to form a shell part. . ≪ / RTI > As described above, the emulsion constituting the emulsion 1 for vibration damper of the present invention is obtained by the multistage polymerization in which the emulsion has the core part and the shell part and then forms the shell part after forming the core part. It is one of the preferred forms of the invention.

In the case of producing an emulsion having the core part and the shell part, a part of the monomer component forming the core part is added to an aqueous solvent such as water to form seed particles, then the remaining monomer component is added to form a core part, , And a method of forming a shell part by adding a monomer component forming the shell part is preferable. Since the average particle diameter of the emulsion is influenced by the number of seed particles in the aqueous medium, the number of seed particles is controlled by suitably adjusting the amount of the monomer component added to the aqueous medium to form the seed particles, The particle diameter can be set within the above-described preferable range.

It is also important to control so as not to generate new particles after generation of the seed particles. In order to produce the above-described emulsion having the above-described particle size distribution of 5 to 40% as the emulsion constituting the vibration damping material for vibration damping material of the present invention, it is necessary to always ensure a reaction rate of a predetermined value or more. Specifically, And the polymerization rate measured after 30 minutes is preferably 80% or more, and more preferably 90% or more.

The aqueous medium is not particularly limited and includes, for example, water, a mixed solvent of one or more kinds of solvents that can be mixed with water, a mixed solvent in which water is a main component, and the like have. Among them, it is preferable to use water.

The amount of the anionic emulsifier and / or reactive emulsifier used is 0.1 to 10% by mass based on the amount of the compound containing the entire polymerizable unsaturated bonding group. If it is less than 0.1% by mass, the mechanical stability can not be sufficiently improved, and the polymerization stability may not be maintained sufficiently. More preferably from 0.5 to 5% by mass, and most preferably from 1 to 3% by mass.

Among the above surfactants, in terms of environment, it is preferable to use a non-nonylphenyl type surfactant.

The amount of the surfactant to be used may be appropriately set depending on the kind of the surfactant to be used and the kind of the monomer component. For example, the amount of the surfactant may be 0.3 to 10 parts by weight based on 100 parts by weight of the total amount of the monomer components used for forming the emulsion And more preferably 0.5 to 5 parts by weight.

Examples of the protective colloid include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol and modified polyvinyl alcohol, cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose salt and the like Derivatives thereof, and natural polysaccharides such as guar gum. One or more of these may be used. The protective colloid may be used alone or in combination with a surfactant.

The amount of the protective colloid to be used may be appropriately set according to the conditions of use and is preferably 5 parts by weight or less based on 100 parts by weight of the total amount of the monomer components used for forming the acrylic copolymer, Is not more than 3 parts by weight.

The polymerization initiator is not particularly limited as long as it is a substance which is decomposed by heat and generates radical molecules, but a water-soluble initiator is preferably used. Examples thereof include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis ), A water-soluble azo compound such as hydrogen peroxide, a thermal decomposition initiator such as hydrogen peroxide, a redox polymerization initiator such as hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide and rhodium, potassium persulfate and metal salts, ammonium persulfate and sodium hydrogen sulfite And one or more of these may be used.

The amount of the polymerization initiator to be used is not particularly limited and may be appropriately set according to the kind of the polymerization initiator. For example, 0.1 to 2 parts by weight per 100 parts by weight of the total amount of the monomer components used for forming the acrylic copolymer More preferably 0.2 to 1 part by weight.

The polymerization initiator may also be used in combination with a reducing agent, if necessary, in order to promote emulsion polymerization. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid and glucose, and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium metabisulfite, May be used alone or in combination of two or more.

The amount of the reducing agent to be used is not particularly limited and is preferably 0.05 to 1 part by weight based on 100 parts by weight of the total amount of the monomer components used for forming the acrylic copolymer.

-메틸스티렌다이머, 터피놀렌,

-테르피넨, γ-테르피넨, 디펜텐, 아니솔, 알릴알코올 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 2 종 이상을 병용해도 된다. 이들 중에서도, 헥실메르캅탄, 옥틸메르캅탄, n-도데실메르캅탄, t-도데실메르캅탄, n-헥사데실메르캅탄, n-테트라데실메르캅탄 등의 알킬메르캅탄류를 사용하는 것이 바람직하다. 중합 연쇄 이동제의 사용량으로는, 예를 들어, 전체 단량체 성분 100 중량부에 대해 통상 2.0 중량부 이하, 바람직하게는 1.0 중량부 이하이다. The polymerization chain transfer agent is not particularly limited and examples thereof include hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan And the like; halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and ethylene bromide; esters such as 2-ethylhexyl mercaptoacetate, 2-ethylhexyl mercaptopropionate, tridecyl ester of mercaptopropionic acid and the like Mercaptocarboxylic acid alkyl esters such as mercaptoacetic acid, methoxybutyl ester of mercaptoacetic acid, alkoxyalkyl ester of mercaptocarboxylic acid such as methoxybutyl ester of mercaptopropionic acid, carboxylic acid mercapto compounds such as 2-mercaptoethyloctanoic acid ester, Alkyl esters,

- methylstyrene dimer, terpinolene,

-Terpinene,? -Terpinene, dipentene, anisole, allyl alcohol and the like. These may be used alone or in combination of two or more. Among these, alkyl mercaptans such as hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan and n-tetradecyl mercaptan are preferably used . The amount of the polymerization chain transfer agent to be used is generally 2.0 parts by weight or less, preferably 1.0 parts by weight or less, based on 100 parts by weight of the total monomer component.

In the emulsion polymerization, a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as sodium polyacrylate, or an inorganic salt may be used if necessary. As a method of adding a monomer component or a polymerization initiator, for example, a batch addition method, a continuous addition method, a multistage addition method and the like can be applied. These addition methods may be appropriately combined.

With respect to the emulsion polymerization conditions in the above production method, the polymerization temperature is not particularly limited, and is preferably, for example, from 0 to 100 캜, more preferably from 40 to 95 캜. The polymerization time is not particularly limited. For example, the polymerization time is preferably 1 to 15 hours, more preferably 5 to 10 hours.

In the method for producing an emulsion constituting the emulsion (1) for vibration damping material of the present invention, it is preferable to neutralize the emulsion with a neutralizing agent after producing the emulsion by emulsion polymerization. As a result, the emulsion is stabilized. The neutralizing agent is not particularly limited, and for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine, ammonia water, sodium hydroxide and the like can be used. These may be used alone or in combination of two or more. Among these, it is preferable to use a volatile base which is volatilized at the time of heating the coating film, because the water resistance and the like of the coating film formed of the vibration damper compound in which the emulsion for vibration damper is essential are improved. More preferably, it is preferable to use an amine having a boiling point of 80 to 360 ° C, since the thermal drying property is improved and the vibration damping property is improved. As such a neutralizing agent, for example, tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine are preferable. More preferably, an amine having a boiling point of 130 to 280 DEG C is used.

The boiling point is a boiling point at normal pressure.

When a neutralizing agent is used in the production of the emulsion 1A for vibration damper of the present invention, the amount of the neutralizing agent to be added is preferably such that the neutralized carboxyl group-containing monomer accounts for 1.0 to 2.0 mol% of the total monomers. When the ratio of the neutralized carboxyl group to the total number of moles of the monomers is within this range, the coating surface does not become insufficient in water retention and the water retention property does not increase, so that the coating film exhibits excellent heat drying performance. The addition amount of the neutralizing agent is more preferably from 1.5 to 2.0 mol% of the neutralized carboxyl group-containing monomer relative to the molar amount of the whole monomers.

When the neutralizing agent is used in the production of the emulsion 1B for vibration damping materials of the present invention, the neutralizing agent is added in an amount of, for example, an acid value of the emulsion, that is, Equivalent to the total amount of water. More preferably 0.8 to 1.2 equivalents.

As described above, by setting the ratio of the neutralized carboxyl group-containing monomer in the monomer component forming the emulsion to the specific range in the emulsion constituting the emulsion 1 for vibration damper of the present invention, Excellent emulsion can be achieved.

An emulsion for vibration damper containing an emulsion obtained by emulsion-polymerizing such a monomer component is obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier. The emulsion is neutralized with respect to the number of moles of all the monomers forming the emulsion An emulsion for vibration damping materials having an average particle diameter of 100 to 450 nm and an amount of the carboxyl group-containing monomer of 1.0 to 2.0 mol% is also one of the present invention.

The emulsion for vibration damping material may be prepared by synthesizing an emulsion and then neutralizing the neutralized carboxyl group-containing monomer so that the neutralized carboxyl group-containing monomer is in the above range with respect to the molar amount of the entire monomers by the addition of the neutralizing agent described above. And synthesizing an emulsion by using a monomer component previously calculated so that the ratio becomes in the above range.

The emulsion (1) for vibration damper of the present invention is characterized in that, when the number average molecular weight is small, in the vibration damper compound containing the emulsion (1) for vibration damper of the present invention in which the emulsion is essential, And the dispersibility is improved.

Next, the emulsion 2 for vibration damping material of the present invention will be described below.

The emulsion (2) for vibration damping material of the present invention contains acrylic emulsion particles having a core portion and a shell portion, but may contain one kind of such emulsion particles or two or more kinds of such emulsion particles. In addition, as long as it contains at least one acrylic emulsion particle having a core part and a shell part, it may contain other emulsion particles other than the acrylic emulsion particle having a core part and a shell part. However, an acrylic emulsion having a core part and a shell part It is preferable that the particles are 50% by mass or more based on 100% by mass of the total amount of the emulsion particles. More preferably, it is 80 mass% or more.

As the emulsion for imparting other emulsion particles, other emulsion resins described later can be used.

The emulsion (2) for a vibration damping material of the present invention contains acrylic emulsion particles having a core part and a shell part. The acrylic emulsion particles exist in the form of an acrylic polymer dispersed in the form of particles in a medium. The medium is preferably an aqueous medium, for example, water or a mixed solvent of water and water mixed with each other, and the like. Among them, water is preferred in view of safety and environmental effects when applying the paint containing the emulsion (2) for vibration damper of the present invention.

The content of the nonvolatile component in the emulsion 2 for vibration damping materials, that is, the content of the acrylic emulsion particles is preferably 30% by mass or more and 70% by mass or less based on 100% by mass of the total amount of the emulsion 2 for vibration damping material. If it exceeds 70% by mass, the viscosity of the emulsion for vibration damper becomes excessively high, and sufficient dispersion stability may not be maintained, which may cause agglomeration. If it is less than 30% by mass, sufficient vibration damping property may not be exhibited. More preferably, it is 50 mass% or more and 65 mass% or less.

When the emulsion (2) for vibration damping material of the present invention contains other emulsion particles other than the acrylic emulsion particles, the total emulsion (2) for vibration damping material of the present invention containing acrylic emulsion particles and other emulsion particles It is preferable that the nonvolatile content of the nonwoven fabric is also the above ratio.

The acrylic emulsion particle contained in the emulsion for vibration damping material (2) of the present invention has a core portion and a shell portion. The core portion and the shell portion may be completely homologous to each other and can not be distinguished from each other. Or a non-homogeneous core / shell composite structure or a microdomain structure.

Of these structures, a core-shell composite structure is preferable in order to sufficiently draw the characteristics of the acrylic emulsion and to produce a stable emulsion.

In the core-shell composite structure, it is preferable that the surface of the core portion is covered with the shell portion. In this case, the surface of the core portion is preferably completely covered with the shell portion, but may not be completely covered. For example, the surface of the core portion may be covered with a mesh or the core portion may be exposed.

The acrylic emulsion particles preferably have an average particle diameter of 100 to 450 nm. If the average particle diameter is less than 100 nm, the viscosity of the emulsion for vibration damper becomes excessively high, or the dispersion stability may not be maintained sufficiently, resulting in agglomeration. If the average particle diameter exceeds 450 nm, the emulsion can not be said to be an emulsion. More preferably 120 to 400 nm, and further preferably 150 to 350 nm.

For example, the emulsion was diluted with distilled water and sufficiently stirred and mixed, and about 10 ml of the emulsion was collected in a glass cell. The particle size was measured with a particle size distribution analyzer ("NICOM P Model 380" manufactured by Particle Sizing Systems, ). ≪ / RTI >

When the emulsion (2) for vibration damping material of the present invention contains other emulsion particles other than the acrylic emulsion particle, the emulsion (2) for vibration damping material of the present invention containing acrylic emulsion particles and other emulsion particles Is also in the above range.

The acrylic emulsion particle preferably has a particle size distribution defined by a value obtained by dividing the standard deviation by the volume average particle diameter (standard deviation / volume average particle diameter x 100) of 40% or less. More preferably, it is 30% or less. When the particle size distribution exceeds 40%, the width of the particle diameter distribution of the emulsion particles becomes very wide, and coarse particles are contained in a part thereof. Therefore, the emulsion exhibits sufficient low-temperature storage stability due to the influence of such coarse particles There is a fear that it will not be able to do.

In the acrylic emulsion having the core part and the shell part, the polymer forming the core part and the polymer forming the shell part are, for example, a weight average molecular weight, a glass transition temperature, an SP value (solubility coefficient) , The use ratio of the monomers, and the like. Among them, as described later, it is preferable that at least one of the weight average molecular weight and the glass transition temperature is different.

The acrylic emulsion is formed by polymerizing a monomer component comprising a (meth) acrylic monomer and a monomer having a Q value in the range of 0.6 to 1.4 and an e value in the range of -0.4 to -1.2. The acrylic monomers and the monomers having Q value and e value within a specific range may be each one, or two or more monomers may be used. The (meth) acrylic monomers and monomers having a Q value and an e value within a specific range may be contained in any of the monomer component forming the core portion of the emulsion and the monomer component forming the shell portion, .

It is preferable that the monomer component contains 0.1 to 20 mass% of a (meth) acrylic acid-based monomer and 99.9 to 80 mass% of other copolymerizable ethylenically unsaturated monomers relative to 100 mass% of the entire monomer component. (Meth) acrylic acid-based monomer, the dispersibility of the filler such as the inorganic powder is improved in the vibration damper blend containing the emulsion (2) for vibration damper of the present invention, and the vibration damping property is further improved. Further, by containing the other copolymerizable ethylenically unsaturated monomer, it is easy to adjust the acid value, Tg, physical properties, and the like of the emulsion. Even if the (meth) acrylic acid-based monomer is less than 0.1% by mass or more than 20% by mass, the emulsion may not be stably copolymerized in the monomer component. In the emulsion of the present invention, the heat drying property and vibration damping property of the water-based vibration damping material can be more fully exhibited by the synergistic effect of the monomer units formed from these monomers.

More preferably 0.5 to 3% by mass of a (meth) acrylic acid-based monomer and 99.5 to 97% by mass of other copolymerizable ethylenically unsaturated monomers relative to 100% by mass of the total monomer component.

Other copolymerizable ethylenically unsaturated monomers include (meth) acrylic monomers other than the acrylic acid monomers described below, unsaturated monomers having nitrogen atoms, styrene monomers, and the like.

The proportion of the (meth) acrylic monomer in the monomer component is preferably 20 to 80% by mass based on 100% by mass of the entire monomer component. More preferably from 30 to 70% by mass.

The ratio of the monomer having the Q value and the e value within a specific range is preferably 20 to 80 mass% with respect to 100 mass% of the total monomer component. More preferably from 30 to 70% by mass, and still more preferably from 40 to 60% by mass.

The (meth) acrylic monomer means a (meth) acrylic acid-based monomer, its salt or esterified product, and the same one as used in the above-described emulsion for vibration damping material (1) can be used. As the (meth) acrylic monomers other than the (meth) acrylic acid monomers, the same ones as those in the above-described emulsion for vibration damping materials (1) can be used.

The monomer component may contain an acrylic monomer, or other monomers other than monomers having a Q value and an e value within a specific range. Examples of other monomers include unsaturated monomers having a nitrogen atom such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide and N-methylol methacrylamide. .

The content of the other monomer is preferably 40 mass% or less, for example, with respect to 100 mass% of the entire monomer component. More preferably, it is 20 mass% or less.

In the acrylic emulsion, the weight average molecular weight of the whole system in which the core part and the shell part are combined is the same as that of the emulsion constituting the above-described emulsion for vibration damping material (1).

When two or more kinds of acrylic emulsions are used as the acrylic emulsion having the core part and the shell part, those having different Tg are preferably used. By forming a difference in the glass transition temperature (Tg) in this manner, higher damping properties can be exhibited under a wide temperature range, and vibration durability particularly in the practical range of 20 to 60 占 폚 is remarkably improved. When three or more kinds of acrylic emulsions are used, at least two acrylic emulsions may be different from each other in Tg, and at least one of the two types of acrylic emulsions may have the same Tg .

(Tg) of the acrylic emulsions (A) and (B) is higher than the glass transition temperature (Tg) of the acrylic emulsions (A) and TgA) and (TgB) are the same as in the case of using two or more kinds of acrylic copolymers having different Tg as the copolymer constituting the above-described emulsion (1) for vibration damping material.

It is preferable that the difference in glass transition temperature (Tg) of the monomer component forming the core part and the monomer component forming the shell part is 10 to 60 캜 in the acrylic emulsion particle. When the difference in Tg is less than 10 占 폚 or when it is larger than 60 占 폚, vibration damping property in a wide temperature range (20 占 폚 to 60 占 폚) can not be obtained. More preferably, the difference in Tg is from 15 to 55 캜, more preferably from 20 to 50 캜. The Tg of the monomer component forming the core portion is preferably higher than the Tg of the monomer component forming the shell portion. That is, in the case of producing an emulsion having a core portion and a shell portion, the emulsion of the core portion is formed and then the emulsion of the shell portion is formed by multi-stage polymerization. Tg of the monomer component used in the shearing process is used Is higher than the Tg of the monomer component. In the case where the emulsion is produced by the three or more steps, it is also preferable that the Tg of the monomer component used in the post-process is lower than the Tg of the monomer component used in the immediately preceding process.

The Tg of the entire acrylic emulsion is preferably -20 to 30 占 폚. More preferably -10 to 20 占 폚, and still more preferably -5 to 10 占 폚.

The Tg of the acrylic emulsion can be determined by the above-described method.

The acrylic emulsion particles preferably have a mass ratio of the monomer component forming the core portion and the monomer component forming the shell portion being 20/80 to 70/30. When the mass ratio of the monomer component forming the core part is smaller than 20/80 or larger than 70/30, the vibration damping property in a wide temperature range can not be obtained.

The preferable values of the pH and viscosity of the acrylic emulsion are the same as those of the emulsion constituting the emulsion 1 for vibration damping material described above.

 The content of the acrylic hard monomer in the monomer component forming the acrylic emulsion particle in the emulsion (2) for vibration damping material of the present invention is preferably 25 mass% or less. The acrylic hard monomer is a monomer having a higher Tg than other monomers in the acrylic monomer component added to prevent mixing of the composition and has a Tg of 30 (preferably 30 to 30), which is higher than the Tg of the whole monomer (also referred to as a soft monomer) other than the hard monomer in the acrylic monomer component Lt; 0 > C or higher. The content of the acrylic hard monomer is more preferably 20 mass% or less, and further preferably 10 mass% or less. The acrylic emulsion particles in the emulsion (2) for vibration damping material according to the present invention contain a monomer having a Q value and an e value within a specific range as a component, so that mixing of the composition of the core / shell structure of the emulsion can be suppressed As a result, it is possible to reduce the amount of the acrylic hard monomer used for suppressing the mixing of such compositions and to reduce the level of vibration damping property of the acrylic emulsion even when the amount of the acrylic hard monomer is reduced. It is possible to produce an acrylic emulsion having a core-shell structure in which mixing of the composition does not occur.

A method for producing an emulsion for vibration damper containing acrylic emulsion particles having a core part and a shell part by using a monomer component in which a monomer having a Q value and an e value within a specific range is essential is also one of the present invention.

As the acrylic hard monomer used for suppressing the mixing of the composition of the core-shell structure of the emulsion, a methacrylic acid ester such as methyl methacrylate is preferable. One or more acrylic hard monomers may be used.

In the emulsion (2) for vibration damping material of the present invention, it is preferable that the monomer having the Q value of forming the acrylic emulsion particle within the range of 0.6 to 1.4 and the e value within the range of -0.4 to -1.2 is a styrene monomer . The number of the substituents and the kind of the substituent are not particularly limited, so long as the styrene monomer is styrene and a derivative thereof and the styrene skeleton is included in the structure, and one or more kinds of substituents can be used.

-아세톡시스티렌, p-아세톡시스티렌, p-클로로메틸스티렌, o-비닐페놀, m-비닐페놀, 2-비닐피리딘, 5-비닐-2-피콜린, 2-이소프로페닐나프탈렌, 2-(o-메틸)-4-비닐카테콜 또는 트리메틸(p-비닐페닐실란) 등이 바람직하다. 보다 바람직하게는 스티렌이다. Examples of the styrenic monomer include styrene, p-methylstyrene, p-tert-butylstyrene, p-methoxystyrene, 3,4-dimethoxystyrene,

2-picoline, 2-isopropenyl naphthalene, 2-vinylphenol, 2-vinylpyridine, 2-vinylpyridine, (o-methyl) -4-vinyl catechol or trimethyl (p-vinylphenyl silane). More preferred is styrene.

In the present invention, it is preferable that the monomer component forming the acrylic emulsion particle contains at least one polymerizable monomer having a glass transition temperature of 0 占 폚 or lower of the homopolymer. More preferably at least two kinds, and most preferably, each of the monomer components used in each step of the multistage polymerization contains one kind of a polymerizable monomer having a glass transition temperature of 0 占 폚 or less of the homopolymer. As the polymerizable monomer having a glass transition temperature of 0 占 폚 or lower of the homopolymer, butyl acrylate and 2-ethylhexyl acrylate are preferable.

That is, in the present invention, it is preferable that the monomer component forming the acrylic emulsion particle is one comprising butyl acrylate and / or 2-ethylhexyl acrylate. If the monomer component comprises butyl acrylate and / or 2-ethylhexyl acrylate, the vibration damping property in a wide temperature range is improved. More preferably, the monomer component contains butyl acrylate and 2-ethylhexyl acrylate.

When the monomer component contains butyl acrylate, when it contains 2-ethylhexyl acrylate, and when it contains both butyl acrylate and 2-ethylhexyl acrylate, The preferable content is the same as the case where the emulsion constituting the above-described emulsion 1 for vibration damping material contains them.

The emulsion (2) for vibration damping material of the present invention is a mixture (blended) with an emulsion for imparting acrylic emulsion particles having a core portion and a shell portion and other emulsion resin. In this case as well, have.

The preferable values of the other emulsion resins and other emulsion resins are the same as those in the case of the emulsion 1 for vibration damping material of the present invention described above.

The emulsion (2) for vibration damper of the present invention is preferably obtained by multi-stage polymerization using a conventional emulsion polymerization method. However, the mode in which the vibration damper emulsion (2) is obtained by multi- It is one of the forms.

The present invention is also a method for producing an emulsion for vibration damper, wherein the emulsion for use in the vibration damping material is produced by a multistage emulsion polymerization process using a monomer component having a different glass transition temperature.

The method for producing the emulsion (2) for vibration damping material is characterized in that the step of performing the emulsion polymerization using the monomer component constituting the core part is carried out at an earlier stage than the step of performing the emulsion polymerization using the monomer component constituting the shell part desirable.

For example, as a method for producing an emulsion for vibration damper, a method for producing the emulsion for vibration damper is a multi-stage emulsion polymerization process using a monomer component having a different glass transition temperature. In the emulsion polymerization process in the first stage, The method for producing the emulsion for vibration damping material is preferably a step for carrying out polymerization by using a monomer component and a step for carrying out polymerization using the monomer component constituting the shell part in the final stage emulsion polymerization step.

(A) a step (a) of forming a core part by emulsion polymerization of a monomer component in an aqueous medium in the presence of a surfactant and / or a protective colloid, (b) (Step (b)) of forming a shell part by emulsion-polymerizing the monomer component in addition to the emulsion contained in the step (b). By such a production method, an emulsion for vibration damper containing particles having a core-shell composite structure can be preferably obtained. Among them, in the above-mentioned production method, in the case of using the polymer constituting the core portion and the polymer constituting the shell portion It is preferable to adjust the hydrophilicity level (SP value) of these acrylic copolymers, the weight average molecular weight of the two, and the like, thereby obtaining an emulsion for vibration damper of the present invention containing particles of an ideal core- .

By the above-described preferred production method, for example, in the step of forming the core part in the step of performing the emulsion polymerization using the monomer component constituting the core part and performing the emulsion polymerization using the monomer component constituting the shell part , The shell portion is formed in contact with the core portion, and the emulsion 2 for vibration damping material of the present invention can be obtained more efficiently. When the emulsion polymerization process of three or more steps is carried out, the first step is a step of carrying out emulsion polymerization using the monomer component constituting the core part, and the final step is carried out by using the monomer component constituting the shell part The emulsion polymerization step between the first step and the last step is not particularly limited as long as it is in the order of the above-mentioned steps.

In each step of the above-mentioned multi-stage polymerization, it is preferable to add a new monomer component after polymerizing at least 80%, more preferably at least 90%, of the monomer components charged at the front end.

Here, the above-mentioned " monomer component having a different glass transition temperature " means a monomer component having a glass transition temperature (absolute temperature) different from that of the homopolymer when the homopolymer (homopolymer) is produced using the monomer component do.

As a method for producing an emulsion having a core portion and a shell portion by the above-mentioned multistage polymerization, a part of a monomer component constituting the core portion is dropped into an aqueous solvent such as water to form seed particles, and then the remaining monomer components are added It is preferable to form the core portion and then add the monomer component constituting the shell portion to form the shell portion. The effect and the specific method obtained by this method are the same as those in the case of using this method in the production of the emulsion constituting the emulsion 1 for vibration damping material of the present invention described above.

The surfactant used in the emulsion polymerization may be any of those conventionally used for emulsion polymerization, and is not particularly limited. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, A polymer surfactant, a reactive surfactant, and the like are preferably used. These can be the same as those used for the production of the emulsion constituting the emulsion for vibration damping material 1 of the present invention.

Among the above surfactants, from the viewpoint of the environment, it is preferable to use a binonylphenyl type surfactant.

The amount of the surfactant to be used may be appropriately set depending on the kind of the surfactant to be used and the kind of the monomer component. For example, the amount of the surfactant may be 0.3 to 10 parts by weight based on 100 parts by weight of the total amount of the monomer components used for forming the emulsion And more preferably 0.5 to 5 parts by weight.

As the protective colloid, the same amount as that used for the production of the emulsion constituting the emulsion for vibration damping material (1) of the present invention may be used in the same amount.

In the method for producing the emulsion (2) for vibration damping material of the present invention, it is preferable to use a polymerization initiator to initiate emulsion polymerization, and a reducing agent may be used in combination if necessary to promote emulsion polymerization. In order to adjust the weight average molecular weight of the acrylic emulsion, it is preferable to use a chain transfer agent in the emulsion polymerization as necessary. As the polymerization initiator, the reducing agent and the chain transfer agent, the same amount as that used in the production of the emulsion constituting the emulsion 1 for vibration damper of the present invention may be used in the same amount.

The method of adding the polymerization temperature, the polymerization time, the monomer components and the polymerization initiator in the method for producing the emulsion for vibration damper 2 is the same as the production of the emulsion constituting the emulsion 1 for the vibration damper of the present invention .

In the method for producing an emulsion constituting the emulsion (2) for vibration damper of the present invention, it is preferable to neutralize the emulsion with a neutralizing agent after the emulsion is produced by emulsion polymerization. As the neutralizing agent, the same ones as used in the production of the emulsion constituting the emulsion 1 for the vibration damping material of the present invention described above can be used.

The addition amount of the neutralizing agent is preferably such that the neutralizing agent base is 0.6 to 1.4 equivalents to the acid value of the emulsion, that is, 1 equivalent of the acid group of the emulsion. More preferably 0.8 to 1.2 equivalents.

In the method for producing the emulsion for vibration damping material (2), the core part and the shell part are basically formed by the same operation. However, the additive and the reaction conditions may be different if necessary. For example, in the emulsion polymerization in the step (b), a surfactant and / or a protective colloid need not be added.

The damping material combination of the present invention is described below.

The emulsions (1) and (2) for vibration damping materials of the present invention can form a vibration damping material combination together with other components as required. The vibration damping material blend containing the emulsion for vibration damping material according to the present invention is also one of the objects of the present invention and is capable of forming an aqueous vibration damping material capable of exhibiting excellent heat drying and vibration damping properties.

It is preferable that the dampening material blend contains, for example, 50 to 90% by mass of solids based on 100% by mass of the total amount of the damping material blend. More preferably from 60 to 90% by mass, and still more preferably from 70 to 90% by mass. In addition, the pH of the vibration damper compound is preferably 7 to 11. And more preferably 7 to 9.

The blending amount of the emulsion 1 and / or the emulsion 1 for vibration damper in the vibration damper combination may be, for example, the emulsion 1 and / or the vibration damper 2 for 100% by mass of the solid content of the vibration damper combination, Is in the range of 10 to 60% by mass. And more preferably 15 to 55 mass%. The solid content of the emulsions 1 and / or 2 for the vibration damper is the mass of the solid content of the emulsion 1 for the vibration damping material and the solid content of the emulsion 2 for the vibration damping material.

The vibration damping properties of the damping material combination can be evaluated by measuring the loss coefficient of the coating formed of the dampening material combination. The loss factor is usually represented by?, Which is the most general index used when exhibiting vibration damping performance, and can be preferably used for evaluating vibration damping performance in the present invention. The higher the numerical value, the better the vibration damping performance. In addition, it is desirable to exhibit a high vibration damping performance within a practical temperature range under the influence of temperature. In the present invention, for example, it is preferable that the practical temperature range of the coating formed from the vibration damper compound is usually 20 to 60 DEG C and the loss factor is 40 to 0.10 or more. And more preferably at least 0.12 at 40 占 폚. Further, in the present invention, for example, since the practical temperature range of the coating film formed of the vibration damper compound is usually 20 to 60 캜, the loss coefficient at 20 캜, 40 캜 and 60 캜 It is appropriate to evaluate the vibration damping performance. That is, the higher the value obtained by summing the loss coefficients at 20 캜, 40 캜 and 60 캜, the better the practical damping performance and is useful as an index for judging damping properties. The preferable range of the value obtained by adding the loss coefficients at 20 占 폚, 40 占 폚 and 60 占 폚 is 0.200 or more, and this value can be sufficiently attained by the present invention. One advantageous effect of the present invention is that it is excellent in mechanical stability, dry film surface condition, and in-film film decaying property (coating film collapsing property after baking) as described above and also in a wide practical temperature range Excellent vibration damping performance can be exhibited, that is, all of these performances can be made excellent.

The values obtained by adding the loss coefficients at 20 캜, 40 캜 and 60 캜 are preferably 0.220 or more by the present invention. A more preferred range is 0.240 or more, and more preferably 0.260 or more.

As a method of measuring the loss coefficient, a resonance method for measurement in the vicinity of a co-frequency is common, and there are a half-width method, a damping ratio method, and a mechanical impedance method. In the damping material combination of the present invention, it is preferable to measure the loss coefficient of the coating formed from the damping material combination as follows. That is, the damping material combination was formed into a coating having a surface density of 4.0 kg / m 2 on a cold-rolled steel sheet (SPCC 15 width x 250 length x thickness 1.5 mm) and cantilever method (loss coefficient measuring system manufactured by Ono Measuring Co., It can be measured by a resonance method (3dB method).

Examples of the other components include solvents, water-based crosslinking agents, plasticizers, stabilizers, thickeners, wetting agents, antiseptics, foaming inhibitors, fillers, coloring agents, dispersants, antirust pigments, antifoaming agents, antioxidants, antifungal agents, And the like can be used. Among them, it is preferable to contain a filler. It is also preferable to contain a pigment (a coloring agent or a rust preventive pigment).

The other components may be mixed with the emulsion for the vibration damping material or the like using, for example, a butterfly mixer, a planetary mixer, a spiral mixer, a kneader, a dissolver or the like.

Examples of the solvent include ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate and the like. The blending amount of the solvent may be suitably set so that the solid content concentration of the emulsion for vibration damper in the vibration damper compound is in the above-mentioned range.

Examples of the water-based crosslinking agent include oxazoline compounds such as Epocres WS-500, WS-700, K-2010, 2020 and 2030 (all trade names, , An epoxy compound such as EM-101-50 (all trade names, manufactured by ADEKA), a melamine compound such as CYMEL C-325 (trade name, manufactured by Mitsui Cytec), a block isocyanate compound, AZO- Mass% zinc oxide aqueous dispersion, manufactured by Nippon Catalyst Co., Ltd.), and the like are preferable. The blending amount of the water-based crosslinking agent is preferably 0.01 to 20 parts by weight, more preferably 0.15 to 15 parts by weight, still more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the solid content of the emulsion for vibration damper, And may be added to the emulsion for vibration damping material or may be added at the same time when other components are blended as the vibration damping material combination.

By mixing the crosslinking agent in the emulsion or the combination for the vibration damping material, the toughness of the resin is improved, and as a result, a sufficient high rigidity is exhibited in the high temperature region. Among them, it is preferable to use an oxazoline compound.

Examples of the thickening agent include polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and the like. The blending amount of the thickener is preferably 0.01 to 2 parts by weight as solid content with respect to 100 parts by weight of the solid content of the emulsion for vibration damper. More preferably 0.05 to 1.5 parts by weight, still more preferably 0.1 to 1 part by weight.

Examples of the filler include calcium carbonate, kaolin, silica, talc, barium sulfate,

Inorganic fillers such as alumina, iron oxide, titanium oxide, glass torch, magnesium carbonate, aluminum hydroxide, diatomaceous earth, talc and clay, scaly inorganic fillers such as glass flakes and mica, fibrous inorganic fillers such as metal oxide whiskers and glass fibers And the like. The blending amount of the inorganic filler is preferably 50 to 700 parts by weight based on 100 parts by weight of the solid content of the emulsion for vibration damper. More preferably 100 to 550 parts by weight.

Examples of the coloring agent include organic or inorganic coloring agents such as titanium oxide, carbon black, spinach, kanji yellow, benzine yellow, phthalocyanine blue, and quinacridone red.

Examples of the dispersing agent include organic dispersants such as inorganic dispersants such as sodium hexametaphosphate and sodium tripolyphosphate, and polycarboxylic acid dispersants.

Examples of the rust preventive pigment include metal phosphate, molybdic acid metal salt and metal borate metal salt.

Examples of the antifoaming agents include silicone antifoaming agents and the like.

It is preferable to use a foaming agent as the other component. In this case, it is preferable that the dampening material composition is heated and dried to form a damping material coating film as described later. By mixing the foaming agent in addition to the above-mentioned emulsion for vibration damping material, effects such as formation of a uniform foaming structure of the vibration damping material and thickening of the damping material are exhibited, and sufficient heat drying and high- do. Thus, the damping material blend containing the emulsion for vibration damper of the present invention and the foaming agent is also one of the preferred embodiments of the present invention. Further, if necessary, other components may be contained.

As the foaming agent, for example, a heat expandable capsule containing a low boiling point hydrocarbon, an organic foaming agent, and an inorganic foaming agent are preferably used, and one or more of these may be used. Examples of the thermal expansion capsules include Matsumoto Microsphere F-30 and F-50 (manufactured by Matsumoto Kasei Co., Ltd.), X-Pantel WU642, WU551, WU461, DU551 and DU401 Examples of the organic foaming agent include azodicarbonamide, azobisisobutyronitrile, N, N-dinitrosopentamethyltetramine, p-toluenesulfonylhydrazine, p-oxybis (benzenesulfohydrazide ), And the like. Examples of the inorganic foaming agent include sodium bicarbonate, ammonium carbonate, silicone hydride, and the like.

The blending amount of the blowing agent is preferably 0.5 to 5.0 parts by weight based on 100 parts by weight of the emulsion for vibration damper. More preferably 1.0 to 3.0 parts by weight.

The vibration damping material blend further containing the blowing agent preferably further comprises an inorganic pigment, and as a result, it is possible to more fully confirm the above-described heat drying property and the manifestation of the high dynamic stability.

As the inorganic pigment, for example, one or more of the above-mentioned inorganic coloring agents and inorganic antirust pigments can be used.

The blending amount of the inorganic pigment is preferably 50 to 700 parts by weight based on 100 parts by weight of the emulsion for vibration damper. More preferably 100 to 550 parts by weight.

As the other component, a polyvalent metal compound may be used. In this case, the multivalent metal compound improves the stability, dispersibility, heat drying property and damping property of the vibration damping material formed from the vibration damping material combination. The polyvalent metal compound is not particularly limited, and examples thereof include zinc oxide, zinc chloride and zinc sulfate, and one or more of these may be used.

The form of the polyvalent metal compound may be, for example, a powder, an aqueous dispersion or an emulsified dispersion. Among them, since the dispersibility into the vibration damper compound improves, it is preferably used in the form of an aqueous dispersion or an emulsion dispersion, more preferably in the form of an emulsion dispersion. The amount of the polyvalent metal compound used is preferably 0.05 to 5.0 parts by weight based on 100 parts by weight of the solid content in the vibration damper combination. More preferably 0.05 to 3.5 parts by weight.

The dampening composition may be applied to a substrate, for example, and dried to form a coating film which becomes a vibration damping material. The substrate is not particularly limited. Further, the method of applying the vibration damper compound to the substrate can be applied by using, for example, a brush, a spatula, an air spray, an airless spray, a mortar gun, a lysine gun and the like.

The application amount of the vibration damper compound may be appropriately set according to the application or desired performance, and it is preferable that the film thickness of the coating film is 0.5 to 8.0 mm when dried. And more preferably 3.0 to 6.0 mm.

It is also preferable to apply the coating so that the surface density of the coating film after drying (after drying) is 1.0 to 7.0 kg / m 2. And more preferably 2.0 to 6.0 kg / m 2. Further, by using the vibration damping material combination of the present invention, it is possible to obtain a coating film which is less likely to cause expansion or cracking during drying, and in which deformation of the paint on the inclined surface is less likely to occur.

In this manner, the coating method is applied so that the film thickness of the coating film at the time of drying is 0.5 to 8.0 mm and dried, and the coating method is applied so that the surface density of the coated film after drying becomes 2.0 to 6.0 kg / The method of applying the damper formulation is also one of the preferred embodiments of the present invention. In addition, the vibration damping material obtained by the method of applying the damping material combination is also one of the preferred embodiments of the present invention.

The conditions for forming the coating film by applying the dampening material combination and then drying may be heat drying or normal temperature drying. However, since the dampening material formulation of the present invention is excellent in thermal drying property, It is preferable to dry it. The heating and drying temperature is preferably 80 to 210 占 폚. More preferably from 110 to 180 占 폚, and still more preferably from 120 to 170 占 폚.

The use of the vibration damping material mixture in which the emulsion for vibration damping material of the present invention is essential can exhibit excellent heat drying and vibration damping properties. Therefore, for example, in addition to the indoor bottom of a car, a railroad vehicle, a ship, an aircraft, Structures, construction equipment, and the like.

Effects of the Invention

The emulsion for vibration damper of the present invention, which is obtained by emulsion polymerization using an anionic emulsifier and contains an emulsion having an emulsion particle having an average particle diameter of 100 to 450 nm, has the above-described constitution, It is possible to improve the vibration damping property, the drying property and the mechanical stability and to improve the coating property on the surface of the coating film and also to the deformation of the coating film even when the coating is applied to the vertical surface and dried by thermal drying using high temperature It is possible to form a good coating film sufficiently suppressed in the collapse of the coating film caused by the vibration damping material of the vibration damping material for the vibration damping material which can be suitably used for various purposes such as a railway vehicle, a ship, an aircraft, an electric appliance, a building structure, Emulsion.

The emulsion for vibration damper of the present invention, which is obtained by emulsion polymerization using a reactive emulsifier and contains an emulsion having an emulsion particle having an average particle diameter of 100 to 450 nm, has the above-mentioned constitution, In addition to being capable of improving the stability and dispersibility of the formulation, it is possible to form a good coating film evenly by coating and drying even when it is applied to an adherend having an inclination Is an emulsion for vibration damping material capable of forming a coating film exhibiting excellent vibration damping property on an inclined surface.

Containing emulsion particles having a core portion and a shell portion formed by polymerizing a monomer component having a Q value in the range of 0.6 to 1.4 and a monomer having an e value in the range of -0.4 to -1.2. The emulsion for vibration damper has the above-described constitution and exhibits high vibration damping property in a wide temperature range, and is excellent in mechanical stability and storage stability at low temperature, and prevents vibration and noise of various structures Which can be preferably used as a material for a vibration damping material.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless specifically stated, "part" means "part by weight" and "%" means "% by mass".

In the following examples, various physical properties and the like were evaluated as follows.

<Tg>

The composition of the monomers used in each stage was calculated from the Fox equation described above. In addition, Tg calculated from the monomer composition used in all stages was described as &quot; total Tg &quot;.

The Tg value of each homopolymer used for calculating the glass transition temperature (Tg) of the polymerizable monomer component by the Fox equation is shown below.

Styrene (St): 100 占 폚

Methyl methacrylate (MMA): 105 DEG C

2-ethylhexyl acrylate (2EHA): - 70 ° C

Acrylic acid (AA): 95 캜

Methacrylic acid (MAA): 130 &lt; 0 &gt; C

n-butyl methacrylate (n-BMA): 20 DEG C

Butyl acrylate (BA): - 56 ° C

Glycidyl methacrylate (GMA): 55 属 C

Hydroxyethyl methacrylate (HEMA): 40 DEG C

<Nonvolatile matter (NV)>

Approximately 1 g of the obtained aqueous resin dispersion was weighed and dried at 110 占 폚 for 1 hour in a hot-air drier. The dried residue was used as nonvolatile matter, and the ratio to mass before drying was expressed as mass%.

<PH>

and the value at 25 캜 was measured by a pH meter ("F-23" manufactured by Horiba Ltd.).

<Viscosity>

B type rotational viscometer under the conditions of 25 캜 and 20 rpm.

&Lt; Minimum Film Production Temperature (MFT) &gt;

The obtained aqueous resin dispersion was applied and dried on a glass plate placed on a thermal gradient tester by a 0.2 mm applicator, and the temperature at which cracks occurred in the coated film was defined as the minimum film forming temperature (MFT).

<Average Particle Diameter, Particle Size Distribution>

The volume average particle diameter was measured using a particle size distribution analyzer (&quot; NICOMP Model 380 &quot; manufactured by Particle Sizing Systems) by a dynamic light scattering method.

Further, a value obtained by dividing the standard deviation by the volume average particle diameter (standard deviation / volume average particle diameter x 100) was calculated as a particle size distribution.

<Reaction rate 1>

The ratio of the actual solid content to the theoretical solid content calculated from the injection amount of the raw material used in the initial polymerization is determined as the reaction rate, Expressed in weight%. When the emulsion to be produced is an emulsion having a core portion and a shell portion which are produced by multi-stage polymerization, the initial portion of the monomer emulsion forming the core portion is used, that is, the addition of the remainder of the monomer emulsion forming the core portion And the ratio of the actual solid content to the theoretical solid content calculated from the injection amount of the raw material used in the initial polymerization was taken as the reaction rate and expressed as% by weight.

 <Reaction rate 2>

When the emulsion to be produced is an emulsion having a core portion and a shell portion produced by multi-stage polymerization, sampling is performed 30 minutes after the end of polymerization at the first stage forming the core portion, and the amount of the raw material The ratio of the measured solid content to the theoretical solid content was expressed as% by weight as a reaction rate.

&Lt; Weight average molecular weight &

Under the following measurement conditions by GPC (gel permeation chromatography).

Measuring instrument: HLC-8120GPC (trade name, manufactured by Toso Co., Ltd.)

Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (all manufactured by Toso Co., Ltd.) are connected in series and used

Eluent: tetrahydrofuran (THF)

Standard material for calibration curve: polystyrene (manufactured by Tosoh Corporation)

Measuring method: The object to be measured was dissolved in THF so that the solid content was about 0.2 mass%, and filtered with a filter, and the molecular weight was measured as a measurement sample.

<Mechanical stability>

30 g of pure water was added to 100 g of the damping material combination, and the mixture was thoroughly stirred and mixed. The mixture was filtered through a 100-mesh metal mesh, and 70 g of the mixture was subjected to a mechanical stability test with a Marron test stability tester (manufactured by Kumagai Rikiki Kogyo Co., Ltd.) Respectively. After the completion of the test, the dampening material mixture was immediately filtered through a 100-mesh metal mesh to obtain a damping material mixture, And dried in an oven at 110 ° C for 1 hour. The coagulation ratio was calculated and evaluated in the following formula.

Aggregation ratio (%) = (mass of metal net after drying (g) - mass (g) of metal net before drying) / 70

Evaluation standard

?: Less than 0.0001%

○: 0.0001% or more and less than 0.001%

?: 0.001% or more and less than 0.01%

×: 0.01% or more and less than 0.1%

&Lt; Surface condition of dry coating film &

The damping material blend prepared on a steel plate (trade name: SPCC-SD 75 mm wide x 150 mm length x 0.8 mm thickness: manufactured by Nippon Test Panel Co., Ltd.) was applied so that the coating thickness of the formulation was 3 mm. Thereafter, the film was dried at 150 DEG C for 30 minutes using a hot-air dryer, and the surface state of the obtained dried film was evaluated by the following criteria.

Evaluation standard

○: No abnormality

Δ: Cracks on the surface or interface

X: Coating film shape can not be maintained

<Test of collapsibility of inner membrane>

A coating composition obtained by the above process was applied to a steel sheet (ED steel plate) of 0.8 * 70 * 150 electrodeposited with Erectron &quot; KG-400 &quot; manufactured by Kansai Paint Co., Ltd. to a wet film thickness of 6 mm. Immediately thereafter, the coated surface was vertically baked at 120 ° C for 30 minutes, and the obtained coating film was visually observed to evaluate the collapsing property of the coating film.

Evaluation standard

The length (mm) in which the paint has collapsed from the top of the coated surface,

?: 0 mm

?: 1 to 2 mm

?: 3 to 5 mm

X: 6 mm or more

&Lt; Test for Drying of Inclined Coating Film &gt;

A coating composition obtained by the above was applied to a steel sheet (ED steel sheet) of 0.8 x 70 x 50 electrodeposited with Erectron &quot; KG-400 &quot; manufactured by Kansai Paint Co., Ltd. to a wet film thickness of 6 mm, (TOUCH MIXER MT-31 manufactured by Yamato Scientific Co., Ltd.) arrived at an angle of approximately 45 ° inclined, and a vibration (60 Hz) was applied at room temperature for 3 minutes. Test was carried out to observe the coating film retentivity, and the dryness of the slant surface coating film was evaluated.

Evaluation standard

The length (mm) in which the paint flows down from the bottom of the coated surface,

O: 0 to 15 mm

?: 16 to 20 mm

X: exceeding 20 mm

<Low temperature storage stability test>

(1) Weigh 200 g of Test Em in 225 cc mayonnaise bottle and cover.

(2) Thereafter, the mixture was allowed to stand in a temperature-controlled constant temperature BOX at -8 DEG C for 16 hours, then left at room temperature for 8 hours, and the emulsion state in the mayonnaise bottle was observed.

The following criterion is used.

○: Not frozen

?: After 16 hours at -8 占 폚, it was frozen, but after 8 hours at room temperature, it was melted

X: Not fused

&Lt; External appearance of coating film &

The damping material mixture thus prepared was applied on a steel plate (trade name: SPCC-SD 75 mm wide x 150 mm length x 0.8 mm thick: manufactured by Nippon Test Panel Co., Ltd.) so that the coating thickness of the formulation was 3 mm. Thereafter, the film was dried at 150 DEG C for 30 minutes using a hot-air dryer, and the swelling and cracking state of the obtained dried film was evaluated by the following criteria.

Evaluation standard

◎: No abnormality

○: A little swelling up and peeling

△: Expansion and peeling are present

X: Coating film shape can not be maintained

<Vibration test>

The vibration damping material blend was applied on a cold rolled steel plate (SPCC 占 15 占 250 占 占 1.5 mm thickness) to a thickness of 3 mm and dried at 150 占 폚 for 30 minutes to obtain a cold-rolled steel sheet having a surface density of 4.0 kg / To form a vibration damper film. The vibration damping property was measured by a cantilever method (loss coefficient measurement system manufactured by Ono Measuring Instrument Co., Ltd.) and the loss coefficient at each temperature (20 ° C to 60 ° C) was measured by the resonance method (3 dB method).

First, the emulsion (1) for vibration damper of the present invention using an anionic emulsifier and / or a reactive emulsifier was tested.

Example 1

A polymerization reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 캜 while stirring under a nitrogen gas stream. On the other hand, 505 parts of styrene, 135.0 parts of 2-ethylhexyl acrylate, 350 parts of butyl acrylate, 10.0 parts of acrylic acid, 4.0 parts of t-dodecyl mercaptan, and 70 parts of Newcol 707SF (trade name, 180.0 parts of polyoxyethylene dicyclohexyl phenyl ether sulfate ammonium salt: manufactured by Nippon Oil &amp; Chemicals Corporation) and 164.0 parts of deionized water were injected. Next, while maintaining the internal temperature of the polymerization reactor at 75 占 폚, 27.0 parts of the monomer emulsion, 5 parts of a 5% potassium persulfate aqueous solution and 10 parts of an aqueous 2% sodium hydrogensulfite solution were added to initiate the initial polymerization. After 40 minutes, while maintaining the inside of the reaction system at 80 占 폚, the remaining monomer emulsion was uniformly added dropwise over 210 minutes. At the same time, 95 parts of a 5% aqueous solution of potassium persulfate and 90 parts of 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 210 minutes, and the same temperature was maintained for 60 minutes after completion of dropwise addition.

After the reaction solution was cooled to room temperature, 16.7 parts of 2-dimethylethanolamine was added to obtain emulsion 1 for vibration damper.

The solid content, pH, viscosity, MFT, average particle diameter, particle size distribution, and weight average molecular weight of the aqueous resin dispersion thus obtained were measured by the above-described method and summarized in Table 1. Examples 2 to 14 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 in the same manner.

Example 2

Emulsion 2 for vibration damping material was obtained in the same manner as in Example 1 except that the emulsifier Newcol 707SF used in Example 1 was changed to ABEX 26-S (trade name, polyoxyethylene alkylphenyl ether sulfuric acid ester salt: manufactured by Rhodia Nikka).

Example 3

Emulsion 3 for vibration damping material was obtained in the same manner as in Example 1 except that the emulsifier Newcol 707SF used in Example 1 was changed to Latex WX (trade name, polyoxyethylene oleyl ether sulfuric acid ester salt: Kao Corporation).

Example 4

Emulsion 4 for vibration damping material was obtained in the same manner as in Example 1 except that the emulsifier Newcol 707SF used in Example 1 was changed to Latex A-E60 (trade name, polyoxyethylene dicyclohexyl ether sulfuric acid ester salt: Kao Company).

Example 5

Emulsion 5 for vibration damping material was obtained in the same manner as in Example 1 except that the emulsifier Newcol 707SF was changed to Hytenol NF-08 (trade name, polyoxyethylene alkyl ether sulfuric acid ester salt: manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.).

Example 6

A polymerization reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 캜 while stirring under a nitrogen gas stream. The dropping funnel was charged with 275 parts of styrene, 1350 parts of 2-ethylhexyl acrylate, 5.0 parts of acrylic acid, 2.0 parts of t-dodecyl mercaptan, 72.0 parts of Latte water WX previously adjusted to 20% aqueous solution and 66.0 parts of deionized water The first stage monomer emulsion was injected. Next, 27.0 parts of the monomer emulsion, 5 parts of a 5% aqueous solution of potassium persulfate and 10 parts of an aqueous solution of 2% sodium hydrogensulfite were added while maintaining the internal temperature of the polymerization reactor at 75 占 폚 to initiate initial polymerization. After 40 minutes, while maintaining the inside of the reaction system at 80 DEG C, the remaining monomer emulsion was uniformly added dropwise over 90 minutes. At the same time, 35 parts of a 5% aqueous solution of potassium persulfate and 30 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 90 minutes, and the same temperature was maintained for 60 minutes after completion of dropwise addition.

Subsequently, a second-stage monomer emulsion composed of 230.0 parts of styrene, 350.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 2.0 parts of t-dodecyl mercaptan, 108.0 parts of Latte water WX previously adjusted to 20% aqueous solution and 98.0 parts of deionized water The mixture was uniformly added dropwise at 80 DEG C over 120 minutes. At the same time, 60 parts of a 5% aqueous solution of potassium persulfate and 60 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 120 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of the dropwise addition.

The obtained reaction solution was cooled to room temperature, and 16.7 parts of 2-dimethylethanolamine was added to obtain emulsion 6 for vibration damper.

Example 7

72.0 parts of the latex WX (20% aqueous solution) used in Example 6 and 24.0 parts of the first stage and 36.0 parts of the second stage of the 108.0 parts used in the second stage were mixed with Emmer 1118S (20% aqueous solution) (Trade name, product name, polyoxyethylene alkyl ether (ethylene oxide: 18 moles): manufactured by Kao Corporation), the same procedure was repeated to obtain emulsion 7 for vibration damping material.

Example 8

Instead of adding 27.0 parts of the monomer emulsion in the first step in Example 6 to the polymerization reactor and performing the initial polymerization, 10 parts of 72.0 parts of a 20% aqueous solution of Latex WX as an emulsifier component was injected into the polymerization reactor, Styrene was replaced with methylmethacrylate in an amount of 230.0 parts of styrene as a second stage monomer component and 350.0 parts of butyl acrylate was changed to 170.0 parts of methyl methacrylate, 310.0 parts of butyl acrylate and 100.0 parts of n-butyl methacrylate. The operation was repeated to obtain emulsion 8 for vibration damping material.

Example 9

The emulsifier Newcol 707SF used in Example 1 was dissolved in 120.0 parts of Hytenol N-08 (20% aqueous solution; product name: polyoxyethylene nonylphenyl ether sulfonate salt: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and Nonipol 200 , Polyoxyethylene nonylphenol ether: manufactured by Sanyo Chemical Industries, Ltd.) was replaced by 60.0 parts, to obtain Emulsion 9 for vibration damping material.

Example 10

Emulsion 10 for vibration damping material was obtained in the same manner as in Example 1 except that 224 parts of deionized water to be injected into the polymerization reactor were replaced by 224 parts and 180.0 parts of Newcol 707SF (20% aqueous solution) was replaced with 360.0 parts.

Example 11

In Example 1, 505 parts of monomer styrene, 135.0 parts of 2-ethylhexyl acrylate, 350 parts of butyl acrylate, and 10.0 parts of acrylic acid were charged in a dropping funnel with 504 parts of styrene, 134.0 parts of 2-ethylhexyl acrylate, and 350 parts of butyl acrylate , And 14.0 parts of methacrylic acid, to obtain emulsion 11 for vibration damping material.

Example 12

An emulsion 12 for vibration damping material was obtained by carrying out the same operation except that the emulsifier Newcol 707SF used in Example 1 was changed to Hytenol N-08.

Example 13

In Example 1, 505 parts of monomer styrene, 135.0 parts of 2-ethylhexyl acrylate, 350 parts of butyl acrylate, and 10.0 parts of acrylic acid were charged in a dropping funnel, 506 parts of styrene, 136.0 parts of 2-ethylhexyl acrylate, and 350 parts of butyl acrylate And 8.0 parts of acrylic acid, the same procedure as in Example 1 was repeated to obtain an emulsion 13 for vibration damper.

Example 14

In Example 1, 505 parts of monomer styrene, 135.0 parts of 2-ethylhexyl acrylate, 350 parts of butyl acrylate and 10.0 parts of acrylic acid, 503 parts of styrene, 134.0 parts of 2-ethylhexyl acrylate, 350.0 parts of butyl acrylate 350 And 13.0 parts of acrylic acid, the same procedure as in Example 1 was repeated to obtain an emulsion 14 for vibration damper.

Example 15

In Example 1, 505 parts of monomer styrene, 135.0 parts of 2-ethylhexyl acrylate, 350 parts of butyl acrylate, 10.0 parts of acrylic acid, 507 parts of styrene, 137.0 parts of 2-ethylhexyl acrylate, 350.0 parts of butyl acrylate 350 And 6.0 parts of acrylic acid, the same procedure as in Example 1 was repeated to obtain emulsion 15 for vibration damper.

Comparative Example 1

The same operation as in Example 1 was repeated except that 27.0 parts of the monomer emulsion to be divided was changed to 2.7 parts to obtain Emulsion 1 for comparison vibration damping material.

Comparative Example 2

In Example 1, 27.0 parts of the monomer emulsion added at 75 deg. C in the polymerization reactor, 5 parts of 5% potassium persulfate aqueous solution and 10 parts of 2% sodium hydrogen sulfite aqueous solution were added instead of the monomer emulsion 1348.0 , And 40 parts of a 5% aqueous solution of potassium persulfate and 40 parts of a 2% aqueous solution of sodium hydrogensulfite were uniformly added dropwise over 150 minutes to obtain an emulsion 2 for a comparative vibration damping material.

Comparative Example 3

The same procedure was repeated except that sodium hydrogensulfite was not used in Example 1 to obtain Emulsion 3 for a comparative vibration damping material.

Comparative Example 4

The procedure of Example 1 was repeated except that 833 g of deionized water to be introduced into the polymerization reactor in Example 1 was replaced by 833 g, 70 g of Newcol 707SF (20% aqueous solution) was added, and 27.0 parts of the monomer emulsion to be divided was changed to 134.8 parts. The same operation was repeated to obtain emulsion 4 for comparison vibration damping material.

Preparation of damping material mixture

The emulsion for vibration damping material obtained in Examples 1 to 15 and Comparative Examples 1 to 4 was blended as described below to evaluate the mechanical stability, the surface condition of the dried coating film, the disintegration resistance and the vibration damping property of the damping material. The results are shown in Tables 1 and 2.

Acrylic copolymer emulsion 359 parts

Calcium carbonate NN # 200^*One 620 part

Dispersant ARC ARIC DL-40S^*2 Part 6

Thickener arc reset WR-650^{* 3} Part 4

Foaming agent Nopko 8034L ^{* 4} Part 1

Foaming agent F-30 ^{* 5} 6 parts

* 1: Filler manufactured by Nitto Kogyo Co., Ltd.

* 2: Special polycarboxylic acid type dispersant (44% active ingredient) manufactured by Nippon Catalyst Co.,

* 3: Alkali-soluble acrylic thickener (30% active ingredient) manufactured by Nippon Kogyo Co.,

* 4: Antifoaming agent (main component: hydrophobic silicone + mineral oil) manufactured by Sanofkobo Co.,

* 5: Foaming agent manufactured by Matsumoto Yushi Co.

Example 16

A polymerization reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 캜 while stirring under a nitrogen gas stream. On the other hand, 505 parts of styrene, 135.0 parts of 2-ethylhexyl acrylate, 350 parts of butyl acrylate, 10.0 parts of acrylic acid, 4.0 parts of t-dodecylmercaptan, (Product name, polyoxyalkylenealkenyl ether sulfuric acid ester salt: manufactured by Kao Corp.) and 164.0 parts of deionized water were injected into the reactor. Next, 27.0 parts of the monomer emulsion, 5 parts of a 5% aqueous solution of potassium persulfate and 10 parts of an aqueous solution of 2% sodium hydrogensulfite were added while maintaining the internal temperature of the polymerization reactor at 75 占 폚 to initiate initial polymerization. After 40 minutes, while maintaining the inside of the reaction system at 80 占 폚, the remaining monomer emulsion was uniformly added dropwise over 210 minutes. At the same time, 95 parts of a 5% aqueous solution of potassium persulfate and 90 parts of an aqueous solution of 2% sodium hydrogensulfite were uniformly added dropwise over 210 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of dropwise addition. After the reaction solution was cooled to room temperature, 16.7 parts of 2-dimethylethanolamine was added to obtain emulsion 16 for vibration damper.

The solid content, pH, viscosity, MFT, average particle diameter, particle size distribution, reaction rate, and weight average molecular weight of the obtained aqueous resin dispersion were measured by the above methods. The ratio (parts by weight) to the total amount of the polymerizable monomers used at both ends of the kind and amount of each polymerizable monomer used is summarized in Table 3. Examples 17 to 29 and Comparative Examples 3 to 4 are shown in Tables 3 and 4 in the same manner.

Example 17

Except that the emulsifier latex PD-104 used in Example 16 was changed to adekariasoft SR-10 (trade name, a sulfuric acid ester salt of allyloxymethylalkoxyethyl polyoxyethylene: ADEKA) An emulsion 17 for vibration damper was obtained.

Example 18

Except that the emulsifier latex PD-104 used in Example 16 was changed to Aquaron KH-10 (trade name, sulfuric acid ester salt of allyloxymethylalkyloxypolyoxyethylene: manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) An emulsion 18 for vibration damper was obtained.

Example 19

Except that the emulsifier latex PD-104 used in Example 16 was changed to Antox MS-60 (trade name, bis (polyoxyethylene dodecylphenyl ether) methacrylate sulfonate salt: manufactured by Nippon Oil &amp; An operation was performed to obtain an emulsion 19 for vibration damper.

Example 20

The same operation was performed except that the emulsifier latex PD-104 used in Example 16 was changed to Adekariosoft SR-30 (trade name, sulfuric acid ester salt of allyloxymethylalkoxyethyl polyoxyethylene: ADEKA) Thereby obtaining an emulsion 20 for vibration damper.

Example 21

A polymerization reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 캜 while stirring under a nitrogen gas stream. On the other hand, 275 parts of styrene, 1350 parts of 2-ethylhexyl acrylate, 5.0 parts of acrylic acid, 2.0 parts of t-dodecyl mercaptan, 72.0 parts of Adekariosoft SR-30 previously adjusted to 20% And 66.0 parts of ionized water were injected into the first-stage monomer emulsion. Next, 27.0 parts of the monomer emulsion, 5 parts of a 5% aqueous solution of potassium persulfate and 10 parts of an aqueous solution of 2% sodium hydrogensulfite were added while maintaining the internal temperature of the polymerization reactor at 75 占 폚 to initiate initial polymerization. After 40 minutes, while maintaining the inside of the reaction system at 80 DEG C, the remaining monomer emulsion was uniformly added dropwise over 90 minutes. At the same time, 35 parts of a 5% aqueous solution of potassium persulfate and 30 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 90 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of dropwise addition.

Subsequently, a mixture of 230.0 parts of styrene, 350.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 2.0 parts of t-dodecyl mercaptan, 108.0 parts of adekarius soap SR-30 previously adjusted to 20% aqueous solution and 98.0 parts of deionized water The monomer emulsion was uniformly added dropwise at 80 DEG C over 120 minutes. At the same time, 60 parts of a 5% aqueous solution of potassium persulfate and 60 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 120 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of the dropwise addition.

After the reaction solution was cooled to room temperature, 16.7 parts of 2-dimethylethanolamine was added to obtain emulsion 21 for vibration damper.

Example 22

72.0 parts of Adderial soap SR-30 (20% aqueous solution) used in Example 21, 72.0 parts of 108.0 parts used in the second step, 24.0 parts of the first step and 36.0 parts of the second step of emulsion 1118S % Aqueous solution) (trade name, polyoxyethylene alkyl ether (ethylene oxide: 18 moles addition): Kao Corporation), to obtain emulsion 22 for vibration damping material.

Example 23

In Example 21, 27.0 parts of the monomer emulsion in the first stage was added to the polymerization reactor and 10 parts of 72.0 parts of a 20% aqueous solution of adekariasoft SR-30 as an emulsifier component was injected into the polymerization reactor , Styrene as the first monomer component was dissolved in methyl methacrylate, 230.0 parts of styrene as the second monomer component, and 350.0 parts of butyl acrylate as 170.0 parts of methyl methacrylate, 310.0 parts of butyl acrylate and 100.0 parts of n-butyl methacrylate The same operation was repeated to obtain the emulsion 23 for vibration damping material.

Example 24

Emulsion 24 for vibration damping material was obtained in the same way as in Example 16 except that 224 parts of deionized water to be fed into the polymerization reactor were replaced with 224 parts and 180.0 parts of the latex PD-104 (20% aqueous solution) was replaced with 360.0 parts.

Example 25

Except that 425 parts of deionized water to be injected into the polymerization reactor in Example 16 was used, and 45.0 parts of 180.0 parts of the used product PD-104 (20% aqueous solution) and 27.0 parts of the monomer emulsion to be separated were changed to 2.7 parts, To obtain an emulsion 25 for vibration damper.

Example 26

Emulsion 26 for vibration damper was obtained by carrying out the same operation except that the emulsifier latex PD-104 used in Example 16 was changed to Hytenol 18E (trade name, polyoxyethylene alkyl ether sulfonate salt: Daiichi Kogyo Seiyaku Co., Ltd.) .

Example 27

The same procedure was repeated except that 60.0 parts of 180.0 parts of Haitenol 18E (20% aqueous solution) used in Example 26 was replaced with Emulgen 1118S (20% aqueous solution) to obtain Emulsion 27 for vibration damper.

Comparative Example 5

The same operation as in Example 16 was repeated, except that 27.0 parts of the monomer emulsion to be divided was changed to 2.7 parts to obtain emulsion 5 for comparison vibration damping material.

Comparative Example 6

Example 16 was repeated except that 833 parts of deionized water to be injected into the polymerization reactor in Example 16 was used, and 70 parts of Latex PD-104 (20% aqueous solution) was injected and 27.0 parts of the monomer emulsion to be divided was changed to 134.8 parts. Was repeated to obtain emulsion 6 for comparison vibration damping material.

Comparative Example 7

In Example 16, instead of adding 27.0 parts of the monomer emulsion added at 75 deg. C in the polymerization reactor, 5 parts of a 5% potassium persulfate aqueous solution and 10 parts of an aqueous 2% sodium hydrogen sulfite solution, the monomer emulsion 1348.0 , And 90 parts of a 5% aqueous solution of potassium persulfate and 90 parts of an aqueous solution of 2% sodium hydrogensulfite were uniformly added dropwise over 150 minutes to obtain an emulsion 7 for a comparative vibration damping material.

Comparative Example 8

The same operation was repeated except that sodium hydrogen sulfite was not used in Example 16 to obtain Emulsion 8 for a comparative vibration damping material.

Preparation of damping material mixture

The emulsions for vibration damper materials obtained in Examples 16 to 27 and Comparative Examples 5 to 8 were blended as follows to evaluate mechanical stability, dryness of the slope surface coating film and vibration damping property as vibration damper blends. The results are shown in Tables 3 and 4.

Acrylic copolymer emulsion 359 parts

Calcium carbonate NN # 200 ^{* 1} 620 parts

Dispersant ARK ARICK DL-40S ^{* 2} Part 6

Thickener arc reset WR-650 ^{* 3} 4 parts

Foaming agent Nopko 8034L ^{* 4} Part 1

Foaming agent F-30 ^{* 5} 6 parts

* 1 to 5 are the same as described above.

Subsequently, the emulsion (2) for vibration damping material of the present invention containing acrylic emulsion particles having a core portion and a shell portion was tested. Also, what is not included in the emulsion for vibration damping material (2) of the present invention is included in the emulsion (1) for vibration damping material of the present invention.

Synthesis of emulsion

Example 28

A polymerization reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 339 parts of deionized water. Thereafter, the internal temperature was raised to 75 캜 while stirring under a nitrogen gas stream. On the other hand, 275 parts of styrene, 135.0 parts of 2-ethylhexyl acrylate, 5.0 parts of acrylic acid, 2.0 parts of t-dodecyl mercaptan and a mixture of 277 parts of styrene, 70 parts of Newcol 707SN (trade name, polyoxyethylene dicyclophenyl 72.0 parts of sodium sulfate of ether (7 moles of ethylene oxide) manufactured by Nippon Oil &amp; Co., Ltd., and 66.0 parts of deionized water was injected into the first stage monomer emulsion. Next, 27.0 parts of the monomer emulsion, 5 parts of a 5% aqueous solution of potassium persulfate and 10 parts of an aqueous solution of 2% sodium hydrogensulfite were added while maintaining the internal temperature of the polymerization reactor at 75 占 폚 to initiate initial polymerization. After 40 minutes, while maintaining the inside of the reaction system at 80 DEG C, the remaining monomer emulsion was uniformly added dropwise over 90 minutes. At the same time, 35 parts of a 5% aqueous solution of potassium persulfate and 30 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 90 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of dropwise addition. The polymerization rate after elapse of 30 minutes after dropping was 95%.

Subsequently, a second-stage monomer emulsion composed of 230.0 parts of styrene, 350.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 2.0 parts of t-dodecyl mercaptan, 108.0 parts of Newcol 707SN previously adjusted to 20% aqueous solution and 98.0 parts of deionized water was mixed with 80 Lt; 0 &gt; C over 120 minutes. At the same time, 60 parts of a 5% aqueous solution of potassium persulfate and 60 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 120 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of the dropwise addition.

The obtained reaction solution was cooled to room temperature, and 16.7 parts of 2-dimethylethanolamine was added to obtain an emulsion 28 for vibration damper. The solid content, pH, viscosity, MFT, average particle diameter, particle size distribution, reaction rate, and weight average molecular weight of the obtained aqueous resin dispersion were measured by the above methods. The ratio (parts by weight) of the polymerizable monomers used in the first and second stages to the total amount of the polymerizable monomers used at both ends was shown in Table 5.

Examples 29 to 40

Emulsions 29 to 40 for vibration damping materials were obtained in the same manner as in Example 28 except that the composition of the aqueous resin in Example 30 was changed to the composition shown in Tables 5 and 6. The calculated Tg, total Tg and other physical properties of each stage are shown in Tables 5 and 6. In the case where the ratios of the first stage and the second stage were different from each other as in Example 36, the loading time of the first stage was 70 minutes, the loading time of the second stage was 140 minutes, the use amount of Newcol 707SN (20% aqueous solution) 60.0 parts in the first stage, 120.0 parts in the second stage, and the reaction time and the amount used were divided according to the proportions of the polymerizable monomer components.

Example 41

In Example 28, the same operations as in Example 28 were repeated, except that 333.0 parts of deionized water was changed to 833.0 parts of deionized water, 70.0 parts of Newcol 707SN (20% aqueous solution) was injected, and 27.0 parts of the monomer emulsion to be divided was changed to 134.8 parts To obtain an emulsion 41 for vibration damping material. The calculated Tg, total Tg and other physical properties of each stage are shown in Table 6.

Example 42

The same operation as in Example 28 was repeated, except that 27.0 parts of the monomer emulsion to be divided was changed to 2.7 parts to obtain an emulsion 42 for vibration damper. The calculated Tg, total Tg and other physical properties of each stage are shown in Table 6.

Examples 43 to 45

Emulsions 43 to 45 for vibration damping materials were obtained in the same manner as in Example 28 except that the composition of the aqueous resin in Example 28 was changed to the compositions shown in Tables 6 and 7. The calculated Tg, total Tg and other properties of each stage are shown in Tables 6 and 7. In the case where the ratios of the first stage and the second stage were different from each other as in Example 36, the loading time of the first stage was 70 minutes, the loading time of the second stage was 140 minutes, the use amount of Newcol 707SN (20% aqueous solution) 60.0 parts in the first stage, 120.0 parts in the second stage, and the reaction time and the amount used were divided according to the proportions of the polymerizable monomer components.

Example 46

20 minutes for the reaction process time of the initial polymerization conducted in Example 28, 60 minutes for the first reaction process time of 90 minutes, 30 minutes for the aging time of 60 minutes after completion of the dropping, 120 minutes of the second reaction process time of 100 Minute, the same operation as in Example 28 was repeated to obtain an emulsion 46 for vibration damper. The calculated Tg, total Tg and other physical properties of each stage are shown in Table 7.

Example 47

27.0 parts of 5% aqueous potassium persulfate solution and 10.0 parts of 2% sodium hydrogen sulfite aqueous solution were added to the first stage monomer emulsion at 75 deg. C in the polymerization reactor in Example 28, and 555.0 parts of monomer emulsion , And simultaneously 40.0 parts of a 5% aqueous solution of potassium persulfate and 40.0 parts of a 2% aqueous solution of sodium hydrogensulfite were added dropwise uniformly over 90 minutes to obtain an emulsion 47 for vibration damper. The calculated Tg, total Tg and other physical properties of each stage are shown in Table 7.

Example 48

The same procedure was repeated except that sodium hydrogen sulfite was not used in Example 28 to obtain an emulsion 48 for vibration damper. The calculated Tg, total Tg and other physical properties of each stage are shown in Table 7.

Example 49

Emulsion 7 for vibration damping material for comparison was obtained in the same manner as in Example 28 except that styrene was not contained as the monomer component. The calculated Tg, total Tg and other physical properties of each stage are shown in Table 7.

Example 50

339.0 parts of deionized water was injected into a polymerization reactor equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel. Thereafter, the internal temperature was raised to 75 캜 while stirring under a nitrogen gas stream. Meanwhile, 450.0 parts of styrene, 190.0 parts of 2-ethylhexyl acrylate, 350.0 parts of butyl acrylate, 10.0 parts of acrylic acid, 5.0 parts of t-dodecyl mercaptan, 180.0 parts of Newcol 707SN previously adjusted to 20% And 164.0 parts of deionized water. Next, 27.0 parts of the monomer emulsion, 5 parts of a 5% aqueous solution of potassium persulfate and 10 parts of an aqueous solution of 2% sodium hydrogensulfite were added while maintaining the internal temperature of the polymerization reactor at 75 占 폚 to initiate initial polymerization. After 40 minutes, while maintaining the inside of the reaction system at 80 占 폚, the remaining monomer emulsion was uniformly added dropwise over 210 minutes. At the same time, 95 parts of a 5% aqueous solution of potassium persulfate and 90 parts of an aqueous solution of 2% sodium hydrogensulfite were uniformly added dropwise over 210 minutes, and the mixture was maintained at the same temperature for 60 minutes after completion of dropwise addition.

The obtained reaction solution was cooled to room temperature, and then 16.7 parts of 2-dimethylethanolamine was added to obtain emulsion 8 for comparison vibration damping material. The solid content, pH, viscosity, MFT, average particle diameter, particle size distribution, reaction rate, and weight average molecular weight of the obtained aqueous resin dispersion were measured by the above method. The ratio (parts by weight) of the polymerizable monomers used in the first and second stages to the total amount of the polymerizable monomers used at both ends in the kind and amount is shown in Table 7.

Preparation of damping material mixture

The emulsion for vibration damper obtained in Examples 28 to 50 was blended as follows, and mechanical stability, low temperature storage stability, appearance of coating film and vibration damping property were evaluated as damping material blends. The results are shown in Tables 5-7.

Acrylic copolymer emulsion 359 parts

Calcium carbonate NN # 200^*One 620 part

Dispersant ARC ARIC DL-40S^*2 Part 6

Thickener arc reset WR-650^{* 3} Part 4

Foaming agent Nopko 8034L^*4 chapter 1

Foaming Agent F-30^{* 5} Part 6

* 1 to 5 are the same as described above.

In Tables 5 to 7, t-DM represents t-dodecyl mercaptan. Other symbols are the same as those described in the description point of the Tg evaluation method described above.

In Tables 5 to 7, Emulsifiers A to F show the following.

A: Newcol 707SN (trade name, sodium sulfate salt of polyoxyethylene dicyclohexylphenyl ether (ethylene oxide 7 mole addition): manufactured by Nippon Oil &amp;

B: ABEX-26S [trade name, sodium sulfate salt of polyoxyethylene alkylphenyl ether (ethylene oxide 26 mole addition): manufactured by Rhodia Nikka Corporation)

C: Adekariosoft SR-30 (trade name, sulfuric acid ester salt of allyloxymethylalkoxyethylpolyoxyethylene (ethylene oxide 30 mole addition): manufactured by ADEKA)

D: Latte water WX (trade name, sodium sulfate salt of polyoxyethylene oleyl ether (ethylene oxide: 23 moles): manufactured by Kao Corp.)

E: Latte water 118B (trade name, sodium sulfate salt of polyoxyethylene alkyl ether (ethylene oxide 18 moles addition) manufactured by Kao Corp.)

 F: EMULGEN 1118S [trade name, polyoxyethylene alkyl ether (ethylene oxide: 18 moles): manufactured by KAO CORPORATION)

Claims (12)

As an emulsion for vibration damper containing an emulsion obtained by emulsion polymerization of a monomer component, The emulsion is obtained by emulsion polymerization using an anionic emulsifier and / or a reactive emulsifier. The emulsion has an average particle diameter of 100 to 450 nm, The emulsion is an emulsion having a core portion and a shell portion, The monomer component contains a monomer having a Q value in the range of 0.6 to 1.4 and an e value in the range of -0.4 to -1.2 in an amount of 30 to 70 mass% based on 100 mass% of the total monomer component, And the content is 10 mass% or less. The method according to claim 1, The emulsion for vibration damper is obtained by emulsion polymerization using an anionic emulsifier. The anionic emulsifier is a sulfate compound or a succinic acid salt compound, Wherein the sulfate compound has at least one group selected from the group consisting of an aliphatic alkyl group having 8 or more carbon atoms, an oleyl group, an alkylphenyl group, a styryl group and a benzyl group. 3. The method of claim 2, The anionic emulsifier may be at least one selected from the group consisting of polyoxyalkylene alkyl ether sulfuric acid ester salts, polyoxyalkylene oleyl ether sulfuric acid sodium salt, polyoxyalkylene alkyl phenyl ether sulfuric acid ester salt, alkyl diphenyl ether disulfonic acid salt, polyoxyalkylene (Mono-, di-, tri-) benzylphenyl ether sulfuric acid ester salt, and alkenyl succinic acid di-salt), a polyoxyalkylene Emulsion for vibration damping material. 3. The method according to claim 1 or 2, Wherein the emulsion has a glass transition temperature of -20 to 30 占 폚. 3. The method according to claim 1 or 2, Wherein the monomer component comprises an unsaturated carboxylic acid monomer. An emulsion for vibration damper containing acrylic emulsion particles having a core part and a shell part, The acrylic emulsion particles are obtained by polymerizing a monomer component containing a monomer having a Q value in the range of 0.6 to 1.4 and an e value in the range of -0.4 to -1.2 in an amount of 30 to 70 mass% based on 100 mass% of the total monomer component Respectively, Wherein the monomer component has a methacrylate ester content of 10 mass% or less. The method according to claim 6, Wherein the acrylic emulsion particle has an average particle diameter of 100 to 450 nm. 8. The method according to claim 6 or 7, Wherein the difference in glass transition temperature between the monomer component forming the core portion and the monomer component forming the shell portion is 10 to 60 占 폚. 8. The method according to claim 6 or 7, Wherein the acrylic emulsion particle has a mass ratio of a monomer component forming the core portion and a monomer component forming the shell portion is 20/80 to 70/30. 8. The method according to claim 6 or 7, Wherein the monomer having a Q value in the range of 0.6 to 1.4 and an e value in a range of -0.4 to -1.2 is the styrene-based monomer. 8. The method according to claim 6 or 7, Wherein the monomer component forming the acrylic emulsion particle comprises butyl acrylate and / or 2-ethylhexyl acrylate. delete